High refraction film, high refraction film-forming coating composition, anti-reflection film, protective film for polarizing plate, polarizing plate and image display device

ABSTRACT

A high refraction film, an anti-reflection film, a protective film for polarizing plate, a polarizing plate and an image display device excellent in weathering resistance are provided. The high refraction film comprises inorganic fine particles having an average particle diameter of from 1 to 200 nm comprising titanium dioxide as a main component and has a refractive index of from 1.55 to 2.40. The anti-reflection film comprises a transparent support and a high refraction film formed thereon. The polarizing plate comprises a polarizing film and two protective films having said polarizing film interposed therebetween, wherein an anti-reflection film is used as at least one of the two protective films or wherein an anti-reflection film is used as one protective film and an optically compensated film having optical isomerism is used as another protective sheet. The image display device has a structure comprising an anti-reflection film or a polarizing plate disposed on the image display surface thereof.

TECHNICAL FIELD

The present invention relates to a high refraction film, a highrefraction film-forming coating composition, and an anti-reflectionfilm, a protective film for polarizing plate, a polarizing plate and animage display device comprising a high refraction film.

BACKGROUND ART

An anti-reflection film is disposed on the display surface of variousimage display devices such as liquid crystal display device (LCD),plasma display panel (PDP), electroluminescence display (ELD) andcathode ray display device (CRT) to inhibit contrast drop due toreflection of external light or image. Therefore, an anti-reflectionfilm is required to have a high physical strength (scratch resistance,etc.), chemical resistance and weathering resistance (resistance tomoist heat, light-resistance, etc.).

As the anti-reflection coat (layer having a laminated structure of highrefraction film, middle refraction film, low refraction film, etc.) tobe used in the anti-reflection film there has heretofore been normallyused a multi-layer coat comprising a lamination of thin transparentfilms of metal oxide. It has been usually practiced to form these thintransparent films of metal oxide by a chemical vapor deposition (CVD)method or physical vapor deposition (PVD) method, particularly vacuumdeposition method, which is one of physical vapor deposition methods.

However, the vacuum deposition method for the formation of thintransparent film of metal oxide gives a low productivity and thus is notsuitable for mass production, and a coating method having a highproductivity has been proposed.

In the case where the anti-reflection film is prepared by a coatingmethod, it is preferred that the high refraction film be prepared byincorporating inorganic fine particles having a high refractive indexdispersed more finely in a film. It is known that when inorganic fineparticles having a high refractive index are incorporated finelydispersed in a film in a larger amount, a transparent high refractionfilm having a higher refractive index is formed (see, for example,JP-A-8-110401, JP-A-8-179123, JP-A-11-153702, JP-A-2001-166104,JP-A-2001-188104, JP-A-2002-116323, and JP-A-2002-156508).

It is also known that the incorporation of titanium dioxide fineparticles having an extremely high refractive index in a high refractionfilm is very effective (see, for example, JP-A-11-153702,JP-A-2001-166104, JP-A-2001-188104, JP-A-2002-116323, andJP-A-2002-156508).

However, in the case where titanium dioxide is used in theanti-reflection film as mentioned above, it is disadvantageous in thatwhen the titanium dioxide fine particles are used under the sunshineover an extended period of time, organic compounds contained in theanti-reflection film are decomposed because the titanium dioxide finepaticles have a photocatalytic action, remarkably deteriorating thephysical strength and optical properties of the anti-reflection film.This phenomenon occurs remarkably particularly with a high refractionfilm having titanium dioxide particles incorporated finely dispersedtherein.

Further, the surface active agent and dispersant which are normally usedas means for dispersing the inorganic fine particles are effective tokeep the inorganic fine particles finely dispersed and hence form atransparent high refraction layer at the step of forming a highrefraction layer, but it is very difficult to provide the highrefraction layer thus obtained with a high physical strength (scratchresistance, etc.), chemical resistance and weathering resistance(resistance to moist heat, light-resistance).

Accordingly, it has been desired to prepare an anti-reflection filmexcellent in physical strength (scratch resistance, etc.), chemicalresistance and weathering resistance (resistance to moist heat,light-resistance) by a coating method, but these requires have neverbeen satisfied sufficiently.

On the other hand, the recent trend is for more liquid crystal displaydevices (LCD) to be provided with a wider screen having ananti-reflection film provided thereon.

A polarizing plate is an indispensable optical material for liquidcrystal display device (LCD) and normally has a polarizing filmprotected by two sheets of protective film.

By providing these protective films with anti-reflection performance,drastic reduction of cost and thickness of display device is madepossible.

The protective film used for polarizing plate needs to be adhesiveenough to be adhered to the polarizing film. As a means for improvingthe adhesiveness to the polarizing film, it has been normally practicedto saponify the protective film, thereby hydrophilizing the surfacethereof.

By effecting the saponification after the formation of ananti-reflection layer on the protective film, cost can be furtherreduced. However, in the case where the anti-reflection film issaponified to give a protective film for polarizing plate, thesaponifying solution further deteriorates the physical strength (scratchresistance, etc.), chemical resistance and weathering resistance(resistance to moist heat, light-resistance) of the high refractionlayer.

DISCLOSURE OF THE INVENTION

The present invention has been worked out in the light of theaforementioned problems with the known technique.

A first object of the present invention is to provide a high refractionfilm excellent in weathering resistance.

A second object of the present invention is to provide a coatingcomposition for forming said high refraction film.

A third object of the present invention is to provide an anti-reflectionfilm and a protective film for polarizing plate excellent in physicalstrength (scratch resistance, etc.), chemical resistance and weatheringresistance (resistance to moist heat).

A fourth object of the present invention is to provide saidanti-reflection film and protective film for polarizing plate in a largeamount at a low price.

A fifth object of the present invention is to provide a polarizing plateand an image display device, which have been subjected toanti-reflection treatment by a proper means.

The above objects are accomplished by a high refraction film, a highrefraction film-forming coating composition, an anti-reflection film, aprotective film for polarizing plate, a polarizing plate and an imagedisplay device having the following constitution.

1. A high refraction film having a refractive index of from 1.55 to 2.40comprising an inorganic fine particles having an average particlediameter of from 1 to 200 nm mainly composed titanium dioxide.

2. A coating composition for forming a high refraction film having arefractive index of from 1.55 to 2.40 comprising an inorganic fineparticles mainly composed of titanium dioxide containing at least oneelement selected from the group consisting of cobalt, aluminum andzirconium.

3. An anti-reflection film comprising a transparent support and a highrefraction film formed thereon.

4. An anti-reflection film comprising a transparent support and at leastone of a high refraction layer and a low refraction layer formedthereon, wherein said high refraction layer is a layer having arefractive index of from 1.55 to 2.40 comprising an inorganic fineparticles mainly composed of titanium dioxide and containing at leastone element selected from the group consisting of cobalt, aluminum andzirconium and said low refraction layer is a layer made of a cured filmcomprising as a main component a copolymer comprising a repeating unitderived from a fluorine-containing vinyl monomer and a repeating unithaving a (meth)acryloyl group in its side chain.

5. A process for the production of the afore-mentioned anti-reflectionfilm.

6. A protective film for polarizing plate comprising a transparentsupport and a high refraction film formed thereon wherein the contactangle of the surface of said transparent support on the side thereofopposite the side having said high refraction film with respect to wateris not greater than 40 degrees.

7. A process for the production of the aforementioned protective filmfor polarizing plate.

8. A polarizing plate comprising a polarizing film and two sheets ofprotective film having said polarizing film interposed therebetweenwherein an anti-reflection film is used as at least one of the twosheets of protective film.

9. A polarizing plate comprising a polarizing film and two sheets ofprotective film having said polarizing film interposed therebetweenwherein an anti-reflection film is used as at least one of the twosheets of protective film and an optically compensated film havingoptical isomerism is used as the other.

10. An image display device having an anti-reflection film or apolarizing plate disposed on the image display surface thereof.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1( a) and (b) each are a schematic sectional view illustratingtypically the layer structure of an anti-reflection film excellent inanti-reflection performance.

FIGS. 2( a) and (b) each are a schematic sectional view illustratingtypically the layer structure of an anti-reflection film further havinganti-glare properties.

FIGS. 3( a) and (b) each are a schematic sectional view illustratingtypically an embodiment of application of an anti-reflection film and aprotective film for polarizing plate to a liquid crystal display device.

FIGS. 4( a) and 4(b) each are a schematic sectional view illustratingtypically an embodiment of application of an anti-reflection film and aprotective film for polarizing plate to a liquid crystal display device.

DESCRIPTION OF REFERENCE NUMERALS AND SIGNS

-   1 Transparent support-   2 Hard coat layer-   3 High refraction film-   4 Low refraction film (outermost layer)-   5 Middle refraction layer-   6 Anti-glare layer-   7 Particles having a refractive index of from 1.40 to 1.80 and an    average particle diameter of from 0.5 to 10 μm-   8 Adhesive layer-   9 Protective film for polarizing plate-   10 Protective film for polarizing plate-   11 Polarizing plate

MODE FOR CARRYING OUT THE INVENTION

The present invention will be further described hereinafter.

High Refraction Film

The high refraction film of the present invention is characterized bythe incorporation of an inorganic fine particles mainly composed oftitanium dioxide containing at least one element selected from the groupconsisting of cobalt, aluminum and zirconium and the exhibition of arefractive index of from 1.55 to 2.40. The high refraction film of thepresent invention is a so-called high refraction film or middlerefraction film and will be hereinafter generically referred to as “highrefraction film”. The refractive index of the high refraction film ispreferably from 1.60 to 2.20, particularly from 1.65 to 2.10. The highrefraction film of the present invention will be further describedhereinafter.

Inorganic Fine Particles Mainly Composed of Titanium Dioxide

The high refraction film of the present invention comprises an inorganicfine particles having as a main component titanium dioxide containing atleast one element selected from the group consisting of cobalt, aluminumand zirconium. The term “main component” as used herein is meant toindicate the highest content (% by weight) in the componentsconstituting the fine particles.

The inorganic fine particles of the present invention mainly composed oftitanium dioxide preferably has a refractive index of from 1.90 to 2.80,more preferably from 2.10 to 2.80, most preferably from 2.20 to 2.80.

The inorganic fine particles of the present invention are capable ofcontrolling the refractive index of the high refraction film as well asinhibiting the cure shrinkage of the film.

The inorganic fine particles mainly composed of titanium dioxide ispreferably kept finely divided in the dispersing medium as much aspossible, and its primary particle preferably has an average particlediameter of from 1 to 200 nm, more preferably from 1 to 150 nm, evenmore preferably from 1 to 100 nm, particularly from 1 to 80 nm. Byfinely dividing the inorganic fine particles to a size of not greaterthan 200 nm, a high refraction film having a desired transparency can beformed.

The particle diameter of the inorganic fine particles can be measured bya light scattering method or electron microphotography. The specificsurface area of the inorganic fine particles is preferably from 10 to400 m²/g, more preferably from 20 to 200 m²/g, most preferably from 30to 150 m²/g.

The content of the inorganic fine particles in the high refraction filmis preferably from 10 to 90% by weight, more preferably from 15 to 80%by weight, particularly from 15 to 75% by weight based on the weight ofthe high refraction film.

Referring to the crystal structure of the inorganic fine particlesmainly composed of titanium dioxide, the main components are preferablyrutile, rutile/anatase mixed crystal, anatase and amorphous structure,particularly rutile structure.

By incorporating at least one element selected from the group consistingof Co (cobalt),Al (aluminum) and Zr (zirconium) in the inorganic fineparticles mainly composed of titanium dioxide, the photocatalyticactivity of titanium dioxide can be inhibited, making it possible toimprove the weathering resistance of the high refraction film of thepresent invention.

Among these elements, at least Co is preferably incorporated in theinorganic fine particles. Further, two or more of the aforementionedelements are used in combination.

Moreover, Co, Al and Zr are preferably present in the form of oxide.

The content of Co, Al and Zr based on Ti (titanium) in the inorganicfine particles is preferably from 0.05 to 30% by weight, more preferablyfrom 0.1 to 10% by weight, even more preferably from 0.2 to 7% byweight, particularly from 0.3 to 5% by weight, most preferably from 0.5to 3% by weight.

Co, Al and Zr are present in the interior or on the surface of theinorganic fine particles mainly composed of titanium dioxide. Co, Al andZr are preferably present in the interior of the inorganic fineparticles mainly composed of titanium dioxide, most preferably both inthe interior and on the surface of the inorganic fine particles mainlycomposed of titanium dioxide.

The presence (e.g., doping) of Co, Al and Zr in the interior of theinorganic fine particles mainly composed of titanium dioxide can beaccomplished by various methods. Examples of these methods include ionimplantation method (Yasushi Aoki, “Hyoumen Kagaku (Surface Science)”,Vol. 18, No. 5, pp. 262-268, 1998), and methods described inJP-A-11-263620, JP-T-11-512336 (“JP-T” means a published Japanesetranslation of a PCT application), EP-A 0 335 773, and JP-A-5-330825.

In particular, a method which comprises introducing Co, Al and Zr in theprocess for the formation of the inorganic fine particles mainlycomposed of titanium dioxide (as described in JP-T-11-512336, EP-A 0 335773, and JP-A-5-330825) is particularly preferred.

The inorganic fine particles comprising titanium dioxide as a maincomponent may further comprise other elements incorporated thereindepending on the purpose. The other elements may be incorporated asimpurities. Examples of the other elements include Sn, Sb, Cu, Fe, Mn,Pb, Cd, As, Cr, Hg, Zn, Mg, Si, P and S.

The inorganic fine particles of the present invention comprisingtitanium dioxide as a main component may be subjected to surfacetreatment in order to lower or eliminate photocatalytic activity oftitanium dioxide. Surface treatment is carried out by the use of aninorganic or organic compound. Examples of the inorganic compound to beused in surface treatment include inorganic compounds containing cobalt(CoO₂, Co₂O₃, Co₃O₄, etc.), inorganic compounds containing aluminum(Al₂O₃, Al(OH)₃, etc.), inorganic compounds containing zirconium (ZrO₂,Zr(OH)₄, etc.), inorganic compound containing silicon (SiO₂, etc.), andinorganic compounds containing iron (Fe₂O₃, etc.).

Particularly preferred among these inorganic compounds are inorganiccompounds containing cobalt, inorganic compounds containing aluminum,and inorganic compounds containing zirconium, most preferably inorganiccompounds containing cobalt, Al(OH)₃, and Zr(OH)₄.

Examples of the organic compound to be used in surface treatment includepolyol, alkanolamine, stearic acid, silane coupling agent, and titanatecoupling agent. The silane coupling agent is mostly preferred. Inparticular, the inorganic fine particles are preferably subjected tosurface treatment with an organic metal compound represented by thefollowing general formula (I) and derivative thereof.(R¹)_(m)—Si(OR²)_(n)  (I)

In the general formula (I), R¹ represents a substituted or unsubstitutedalkyl group or aryl group. R² represents a substituted or unsubstitutedalkyl group or acyl group. The suffix m represents 0 or an integer offrom 1 to 3 and the suffix n represents an integer of from 1 to 4, withthe proviso that the sum of m and n is 4.

In the general formula (I), R¹ represents a substituted or unsubstitutedalkyl group or aryl group. Examples of the alkyl group include methylgroup, ethyl group, propyl group, isopropyl group, hexyl group, t-butylgroup, sec-butyl group, hexyl group, decyl group, hexadecyl group, etc.The number of carbon atoms in the alkyl group represented by R¹ ispreferably from 1 to 30, more preferably from 1 to 16, particularly from1 to 6. Examples of the aryl group represented by R¹ include phenylgroup, naphthyl group, etc. Preferred among these aryl groups is phenylgroup.

The substituents are not specifically limited but are preferably halogenatoms (fluorine, chlorine, bromine, etc.), hydroxyl groups, mercaptogroups, carboxyl groups, epoxy groups, alkyl groups (methyl group, ethylgroup, i-propyl group, propyl group, t-butyl group, etc.), aryl groups(phenylgroup, naphthyl group, etc.), alkoxy groups (methoxy, ethoxy,i-propoxy group, hexyloxy group, etc.), aryloxy groups (phenoxy group,etc.), alkylthio groups (methylthio group, ethylthio group, etc.),arylthio groups (phenylthio group, etc.), alkenyl groups (vinyl group,1-propenyl group, etc.), alkoxysilyl groups (trimethoxysilyl group,triethoxysilyl group, etc.), acyloxy groups (acetoxy group,(meth)acryloyl group, etc.), alkoxycarbonyl groups (methoxycarbonylgroup, ethoxycarbonyl group, etc.), aryloxycarbonyl groups(phenoxycarbonyl group, etc.), carbamoyl groups (carbamoyl group,N-methylcarbamoyl group, N,N-dimethylcarbamoyl group,N-methyl-N-octylcarbamoyl group, etc.), acylamino groups (acetylaminogroup, benzoylamino group, acrylamino group, methacrylamino group,etc.), etc.

Even more desirable among these groups are hydroxyl groups, mercaptogroups, carboxyl groups, epoxy groups, alkyl groups, alkoxysilyl groups,acyloxy groups, and acrylamino groups. Particularly preferred amongthese groups are epoxy groups, polymerizable acyloxy groups((meth)acryloyl group, etc.), and polymerizable acylamino groups(acrylamino group, methacrylamino group, etc.). These substituents maybefurther substituted.

R² represents a substituted or unsubstituted alkyl group or acyl group.The description of the alkyl group, acyl group and substituents is thesame as in R¹. R² is preferably an unsubstituted alkyl group orunsubstituted acyl group, particularly unsubstituted alkyl group.

The suffix m represents 0 or an integer of from 1 to 4. The sum of m andn is 4. When there are a plurality of R¹'s or R²'s, the plurality ofR¹'s or R²'s maybe the same or different. The suffix m is preferably 0,1 or 2, particularly 1.

Specific examples of the compound represented by the general formula (I)will be shown below, the present invention is not limited thereto.

Particularly preferred among these specific examples are compounds (1),(12), (18), (19), etc.

The content of the compound of the general formula (I) is preferablyfrom 1 to 90% by weight, more preferably from 2 to 80% by weight,particularly from 5 to 50% by weight of the total solid content in thehigh refraction film.

Examples of the titanate coupling agent include metal alkoxides such astetraisopropoxytitanium, e.g., tetamethoxytitanium, tetraethoxytitanium, PLENACT (KR-TTS, KR-46B, KR-55, KR-41B, etc., produced byAjinomoto Co., Ltd.), etc.

Preferred examples of the organic compound to be used in surfacetreatment include polyol, alkanolamine, and other organic compoundshaving anionic group. Particularly preferred among these organiccompounds are organic compounds having carboxyl group, sulfonate groupor phosphate group.

Stearic acid, lauric acid, oleic acid, linoleic acid, linolenic acid,etc. are preferably used.

The organic compound to be used in surface treatment preferably furtherhas a crosslinkable or polymerizable functional group. Examples of thecrosslinkable or polymerizable functional group include ethylenicallyunsaturated groups which can undergo addition reaction/polymerizationreaction of radical seeds (e.g., (meth)acrylic group, allyl group,styryl group, vinyloxy group), cationically-polymerizable groups (epoxygroup, oxatanyl group, vinyloxy group), polycondensation-reactive groups(hydrolyzable silyl group, N-methylol group, etc.), etc. Preferably,groups having ethylenically unsaturated group are used.

Two or more of the above-described surface treatment methods may beconducted in combination. It is particularly preferred that an inorganiccompound containing aluminum and an inorganic compound containingzirconium be used in combination.

The inorganic fine particles of the present invention mainly composed oftitanium dioxide may be subjected to surface treatment to have acore/shell structure as described in JP-A-2001-166104.

The shape of the inorganic fine particles mainly composed of titaniumdioxide to be incorporated in the high refraction film is preferablyrice grain-shaped, spherical, cubic, spindle-shaped or amorphous,particularly amorphous or spindle-shaped.

Two or more kinds of inorganic fine particless may be incorporated incombination in the high refraction film.

Dispersant

For the dispersion of the inorganic fine particles mainly composed oftitanium dioxide to be used in the high refraction film of the presentinvention, a dispersant may be used.

For the dispersion of the inorganic fine particles mainly composed oftitanium dioxide of the present invention, a dispersant having ananionic group is preferably used.

As the anionic group, a group having an acidic proton such as carboxylgroup, sulfonate group (sulfo), phosphate group (phosphono) andsulfonamide group or salt thereof is useful. In particular, carboxylgroup, sulfonate group, phosphate group or salt thereof is preferred,particularly carboxyl group or phosphate group. The number of anionicgroups to be contained per molecule of dispersant may be one or more.

For the purpose of further improving the dispersibility of the inorganicfine particles, a plurality of anionic groups may be incorporated in thedispersant. The number of anionic groups to be contained in thedispersant is preferably two or more, more preferably five or more,particularly 10 or more on the average. A plurality of kinds of anionicgroups may be contained per molecule of dispersant.

The dispersant may contain a crosslinkable or polymerizable functionalgroup. Examples of the crosslinkable or polymerizable functional groupinclude ethylenically unsaturated groups which can undergo additionreaction/polymerization reaction of radical seeds (e.g., (meth)acrylicgroup, allyl group, styryl group, vinyloxy group),cationically-polymerizable groups (epoxy group, oxatanyl group, vinyloxygroup), polycondensation-reactive groups (hydrolyzable silyl group,N-methylol group, etc.), etc. Preferably, groups having ethylenicallyunsaturated group are used.

The dispersant which is preferably used in the dispersion of theinorganic fine particles mainly composed of titanium dioxide to be usedin the high refraction film of the present invention is a dispersanthaving an anionic group and a crosslinkable or polymerizable functionalgroup and having the crosslinkable or polymerizable functional group inits side chain.

The weight-average molecular weight (Mw) of the dispersant having ananionic group and a crosslinkable or polymerizable functional group andhaving the crosslinkable or polymerizable functional group in its sidechain is not specifically limited but is preferably not smaller than1,000. The weight-average molecular weight (Mw) of the dispersant ismore preferably from 2,000 to 1,000,000, even more preferably from 5,000to 200,000, particularly from 10,000 to 100,000.

The dispersant having an anionic group and a crosslinkable orpolymerizable functional group and having the crosslinkable orpolymerizable functional group in its side chain preferably has theaforementioned anionic group in its side chain or at the terminal endthereof. Referring to the method for incorporating the anionic group inthe side chain, synthesis may be carried out by the use of polymerreaction such as method involving the polymerization of monomer (e.g.,(meth)acrylic acid, maleic acid, partly-esterified maleic acid, itaconicacid, crotonic acid, 2-carboxyethyl(meth)acrylate, 2-sulfoethyl(meth)acrylate, mono-2-(meth)acryloyloxyethyleester phosphate) andmethod involving the reaction of a polymer having an amino group or thelike with an acid anhydride.

The content of the anionic group-containing polymer unit in thedispersant having an anionic group in its side chain is from 10⁻⁴ to 100mol %, preferably from 1 to 50 mol %, particularly from 5 to 20 mol %based on the total polymer unit.

On the other hand, referring to the method for incorporating an anionicgroup in the dispersant at the terminal thereof, synthesis may becarried out by the use of a method involving the polymerization reactionin the presence of an anionic group-containing chain transfer agent(e.g., thioglycolic acid), a method involving the polymerizationreaction in the presence of an anionic group-containing polymerizationinitiator (e.g., V-501, produced by Wako Pure Chemical Industries, Ltd.)or the like.

A particularly preferred dispersant is a dispersant having an anionicgroup in its side chain.

Examples of the crosslinkable or polymerizable functional group includeethylenically unsaturated groups which can undergo additionreaction/polymerization reaction of radical seeds (e.g., (meth)acrylicgroup, allyl group, styryl group, vinyloxy group),cationically-polymerizable groups (epoxy group, oxatanyl group, vinyloxygroup), polycondensation-reactive groups (hydrolyzable silyl group,N-methylol group, etc.), etc. Preferably, groups having ethylenicallyunsaturated group are used.

The number of crosslinkable or polymerizable functional groups to beincorporated per molecule of dispersant is preferably two or more, morepreferably five or more, particularly ten or more on the average. Aplurality of crosslinkable or polymerizable functional groups may beincorporated per molecule of dispersant.

As the polymer unit having ethylenically unsaturated groups in its sidechain in the preferred dispersant of the present invention there may beused a polymer unit having a poly-1,2-butadiene or poly-1,2-isoprenestructure or (meth)acrylic acid ester or amide polymer unit having aspecific residue (R in —COOR or —CONHR) bonded thereto. Examples of theaforementioned specific residue (R group) include —(CH₂)_(n)—CR₁═CR₂R₃,—(CH₂O)_(n)—CH₂CR₁═CR₂R₃, —(CH₂CH₂O)_(n)—CH₂CR₁═CR₂R₃,—(CH₂)_(n)—NH—CO—O—CH₂CR₁═CR₂R₃, —(CH₂)_(n)—O—CO—CR₁═CR₂R₃, and—(CH₂CH₂O)₂—X (in which R₁ to R₃ each represent a hydrogen atom, halogenatom, C₁-C₂₀ alkyl group, aryl group, alkoxy group or aryloxy group, R₁and R₂ or R₃ may be connected to each other to form a ring, n representsan integer of from 1 to 10, and X represents a dicyclopentadienylresidue). Specific examples of the ester residue include —CH₂CH═CH₂(corresponding to polymer of allyl(meth)acrylate described inJP-A-64-17047), —CH₂CH₂O—CH₂CH═CH₂, —CH₂CH₂OCOCH═CH₂,—CH₂CH₂OCOC(CH₃)═CH₂, —CH₂C(CH₃)═CH₂, —CH₂CH═CH—C₆H₅,—CH₂CH₂OCOCH═CH—C₆H₅, —CH2CH2-NHCOO—CH2CH═CH2, and —CH₂CH₂O—X (in whichX represents a dicyclopentadienyl residue). Specific examples of theamide residue include —CH₂CH═CH₂, —CH₂CH₂—Y (in which Y represents a1-cyclohexenyl residue), —CH₂CH₂—OCO—CH═CH₂, and —CH₂CH₂—OCO—C(CH₃)═CH₂.

The afore-mentioned dispersant having an ethylenically unsaturated groupundergoes addition of free radical (polymerization initiating radical orgrowing radical in the process of polymerization of polymerizablecompound) to the unsaturated connecting group and hence additionpolymerization of the molecules themselves or via polymer chain ofpolymerizable compound so that the molecules are crosslinked to causecuring. Alternatively, the afore-mentioned dispersant undergoes removalof atoms (e.g., hydrogen atom on the carbon atom adjacent to theunsaturated connecting group) with a free radical to produce polymerradicals which are then connected to each other to crosslink themolecules, resulting in the curing of the dispersant.

Referring to the method for incorporating a crosslinkable orpolymerizable functional group in the side chain, synthesis may becarried out by the use of a method involving the copolymerization ofcrosslinkable or polymerizable functional group-containing monomers(e.g., allyl(meth)acrylate, glycidiyl(meth)acrylate,trialkoxysilylpropyl methacrylate), the copolymerization of butadiene orisoprene or the copolymerization of vinyl monomers having 3-chloropionicacid ester site followed by dehydrochlorination as described inJP-A-3-249653, a method involving the incorporation of crosslinkable orpolymerizable functional groups by polymer reaction (e.g., polymerreaction of epoxy group-containing vinyl monomer into carboxylgroup-containing polymer) or the like.

The unit containing a crosslinkable or polymerizable functional groupmay constitute all the polymer units other than the anionicgroup-containing polymer unit but preferably accounts for from 5 to 50mol %, particularly from 5 to 30 mol % of all the crosslinkable orpolymerizable units.

The preferred dispersant of the present invention may be a copolymerwith a proper monomer other than the monomers having a crosslinkable orpolymerizable functional group and anionic group. The copolymercomponents are not specifically limited but are selected from variousstandpoints such as dispersion stability, compatibility with othermonomer components and strength of resulting film. Preferred examples ofthe copolymer components include methyl(meth)acrylate,n-butyl(meth)acrylate, t-butyl(meth)acrylate, cyclohexyl(meth)acrylate,styrene, etc.

Preferred embodiments of the dispersant of the present invention are notspecifically limited but are preferably block copolymers or randomcopolymers, particularly random copolymers from the standpoint of costand ease of synthesis.

Specific preferred examples of the dispersant of the present inventionwill be given below, but the present invention is not limited thereto.These examples represent random copolymers unless otherwise specified.

-   -   The x/y/z ratio indicates molar ratio.

x y z R Mw P-(1) 80 20  0 — 40,000 P-(2) 80 20  0 — 110,000 P-(3) 80 20 0 — 10,000 P-(4) 90 10  0 — 40,000 P-(5) 50 50  0 — 40,000 P-(6) 30 2050 CH₂CH₂CH₃ 30,000 P-(7) 20 30 50 CH₂CH₂CH₂CH₃ 50,000 P-(8) 70 20 10CH(CH₃)₃ 60,000 P-(9) 70 20 10

150,000 P-(10) 40 30 30

15,000

A Mw P-(11)

20,000 P-(12)

30,000 P-(13)

100,000 P-(14)

20,000 P-(15)

50,000 P-(16)

15,000

A Mw P-(17)

20,000 P-(18)

25,000 P-(19)

18,000 P-(20)

20,000 P-(21)

35,000

R¹ R² x y z Mw P-(22)

C₄H₉ (n) 10 10 80 25,000 P-(23)

C₄H₉ (t) 10 10 80 25,000 P-(24)

C₄H₉ (n) 10 10 80 500,000 P-(25)

C₄H₉ (n) 10 10 80 23,000 P-(26)

C₄H₉ (n) 80 10 10 30,000 P-(27)

C₄H₉ (n) 50 20 30 30,000 P-(28)

C₄H₉ (t) 10 10 80 20,000 P-(29)

CH₂CH₂OH 50 10 40 20,000 P-(30)

C₄H₉ (n) 10 10 80 25,000 P-(31)

Mw = 60,000 P-(32)

Mw = 10,000 P-(33)

Mw = 20,000 P-(34)

Mw = 30,000(Block copolymer) P-(35)

Mw = 15,000(Block copolymer) P-(36)

Mw = 8,000 P-(37)

Mw = 5,000 P-(38)

Mw = 10,000

The amount of the inorganic fine particles to be used is preferably from1 to 50% by weight, more preferably from 5 to 30% by weight, mostpreferably from 5 to 20% by weight based on the dispersant. Two or morekinds of dispersant may be used in combination.

High Refraction Film and its Forming Method

The inorganic fine particles comprising titanium dioxide as a maincomponent to be used in the high refraction film is used in the form ofdispersion to form a high refraction film. For the dispersion of theinorganic fine particles, the inorganic fine particles are dispersed ina dispersing medium in the presence of the aforementioned dispersant.

As the dispersing medium there is preferably used a liquid having aboiling point of from 60° C. to 170° C. Examples of the dispersingmedium include water, alcohols (e.g., methanol, ethanol, isopropanol,butanol, benzyl alcohol), ketone (e.g., acetone, methyl ethyl ketone,methyl isobutyl ketone, cyclohexanone), esters (e.g., methyl acetate,ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethylformate, propyl formate, butyl formate), aliphatic hydrocarbons (e.g.,hexane, cyclohexane), halogenated hydrocarbons (e.g., methylenechloride, chloroform, carbon tetrachloride), aromatic hydrocarbons(e.g., benzene, toluene, xylene), amides (e.g., dimethylformamide,dimethylacetamide, n-methylpyrrolidone), ethers (e.g., diethyl ether,dioxane, tetrahydrofurane), and ether alcohols (e.g.,1-methoxy-2-propanol). Toluene, xylene, methyl ethyl ketone, methylisobutyl ketone, cyclohexanone and butanol are preferred.

Particularly preferred dispersing media are methyl ethyl ketone, methylisobutyl ketone, and cyclohexanone.

The inorganic fine particles are dispersed using a dispersing machine.Examples of the dispersing machine include sand grinder mill (e.g., beadmill with pin), dynomill, high speed impeller mill, pebble mill, rollermill, attritor, and colloid mill. Sand grinder mill, dynomill, and highspeed impeller mill are particularly preferred. Further, preliminarydispersion treatment may be effected. Examples of the dispersing machineto be used in preliminary dispersion treatment include ball mill,three-roll mill, kneader, and extruder.

The high refraction film to be used in the present invention ispreferably formed by adding to a dispersion obtained by dispersing theinorganic fine particles in a dispersing medium as mentioned abovepreferably a binder precursor required for the formation of a matrix(e.g., ionizing radiation-curing polyfunctional monomer orpolyfunctional oligomer described later), a photopolymerizationinitiator, etc. to form a coating composition for forming a highrefraction film, applying the coating composition for forming a highrefraction film to a transparent support, and then subjecting theionizing radiation-curing compound (e.g., polyfunctional monomer orpolyfunctional oligomer) to crosslinking reaction or polymerizationreaction to cause curing.

Further, the binder contained in the coating composition for forming ahigh refraction film is preferably allowed to undergo crosslinkingreaction or polymerization reaction with the dispersant at the same timewith or after the application of the film.

Referring particularly to the binder in the high refraction film, theaforementioned preferred dispersant and the ionizing radiation-curingpolyfunctional monomer or polyfunctional oligomer are subjected tocrosslinking or polymerization reaction to cause the anionic group inthe dispersant to be captured in the binder. The binder in the highrefraction film has a function of allowing the anionic group to keep theinorganic fine particles dispersed. The crosslinked or polymerizedstructure renders the binder capable of forming a film, improving thephysical strength, chemical resistance and weathering resistance of thehigh refraction film containing the inorganic fine particles.

The functional group in the ionizing radiation-curing polyfunctionalmonomer or polyfunctional oligomer is preferably a photopolymerizable,electron ray-polymerizable or radiation-polymerizable, particularlyphotopolymerizable functional group.

Examples of the photopolymerizable functional group include unsaturatedpolymerizable functional groups such as (meth)acryloyl group, vinylgroup, styryl group and allyl group, etc. Preferred among thesephotopolymerizable functional groups is (meth)acryloyl group.

Specific examples of the photopolymerizable polyfunctional monomerhaving a photopolymerizable functional group include (meth)acrylic aciddiesters of alkylene glycol such as neopentyl glycol acrylate,1,6-hexanediol(meth)acrylate and propylene glycol di(meth)acrylate,(meth)acrylic acid diesters of polyoxyalkylene glycol such astriethyleneglycol di(meth)acrylate, dipropyleneglycol di(meth)acrylate,polyethyleneglycol di(meth)acrylate and polypropyleneglycoldi(meth)acrylate, (meth)acrylic acid diesters of polyvalent alcohol suchas pentaerythritol di(meth)acrylate, (meth)acrylic acid diesters ofethylene oxide or propylene oxide adduct such as2,2-bis{4-(acryloxy.diethoxy)phenyl}propane and2-2-bis{4-(acryloxy.polypropoxy)phenyl}propane, etc.

Further, epoxy(meth)acrylates, urethane(meth)acrylates andpolyester(meth)acrylates are preferably used as photopolymerizablepolyfunctional monomers.

In particular, esters of polyvalent alcohol with (meth)acrylic acid arepreferred. Even more desirable are polyfunctional monomers having threeor more (meth)acryloyl groups per molecule. Specific examples of thesepolyfunctional monomers include trimethylolpropane tri(meth)acrylate,trimethylolethane tri(meth)acrylate, 1,2,4-cyclohexanetetra(meth)acrylate, pentaglycerol triacrylate, pentaerythritoltetra(meth)acrylate, pentaerythritol(meth)acrylate, (di)pentaerythritoltriacrylate, (di)pentaerythritol pentaacrylate, (di)pentaerythritoltetra(meth)acrylate, (di)pentaeruthritol hexa(meth)acrylate,tripentaeruthritol triacrylate, tripentaethritol hexatriacrylate, etc.

Two or more kinds of polyfunctional monomer may be used in combination.

The polymerization reaction of the photopolymerizable polyfunctionalmonomer is preferably effected in the presence of a photopolymerizationinitiator. Preferred examples of the photopolymerization initiatorinclude photoradical polymerization initiator and photocationicpolymerization initiator. Particularly preferred among thesephotopolymerization initiators is photoradical polymerization initiator.

Examples of the photoradical polymerization initiator includeacetophenones, benzophenones, Michler's benzoyl benzoate,α-amyloximester, tetramethylthiuram monosulfide, thioxanthones, etc.

Examples of commercially available photoradical polymerizationinitiators include KAYACURE (DETX-S, BP-100, BDMK, CTX, BMS, 2-EAQ, ABQ,CPTX, EPD, ITX, QTX, BTC, MCA, etc.), produced by NIPPON KAYAKU CO.,LTD., Irgacure (651, 184, 500, 907, 369, 1173, 2959, 4265, 4263, etc.),produced by Cibasophy Ciba-Geigy Japan Limited, Esacure (KIP100F, KB1,EB3, BP, X33, KT046, KT37, KIP150, TXT), produced by Sartomer Company,etc.

In particular, photo-cleavable photoradical polymerization initiatorsare preferred. These photo-cleavable photoradical polymerizationinitiators are described in Kazuhiro Takabo, “Saishin UV Koka gijutsu(Modern UV Curing Technology)”, K. K. Gijutsu Joho Kyokai, page 159,1991.

Examples of commercially available photo-cleavable photoradicalpolymerization initiators include Irgacure (651, 184, 907), produced byCibasophy Ciba-Geigy Japan Limited, etc.

The photopolymerization initiator is preferably used in an amount offrom 0.1 to 15 parts by weight, more preferably from 1 to 10 parts byweight based on 100 parts by weight of the polyfunctional monomer.

In addition to the photopolymerization initiator, a photosensitizer maybe used. Specific examples of the photosensitizer include n-butylamine,triethylamine, tri-n-butylphosphine, Michler's ketone, and thioxanthone.

Examples of commercially available photosensitizers include KAYACURE(DMBI, EPA), produced by NIPPON KAYAKU CO., LTD., etc.

The photopolymerization reaction is preferably carried out byirradiation with ultraviolet rays after the application and drying ofthe high refraction film.

The high refraction film to be used in the present invention can alsocontain the compound represented by the general formula (I) and/orderivative compound thereof as decribed hereinbefore, that are thecompounds used for surface treatment of the inorganic fine particles.

In this embodiment, the content of the compound of the general formula(I) is also preferably from 1 to 90% by weight, more preferably from 2to 80% by weight, particularly from 5 to 50% by weight based on thetotal solid content in the high refraction film Further, compounds (1),(12), (18), (19) and the like are particularly preferably used.

The binder contained in the high refraction film of the presentinvention preferably further has a silanol group. The furtherincorporation of a silanol group in the binder makes it possible tofurther improve the physical strength, chemical resistance andweathering resistance of the high refraction film.

The silanol group can be incorporated in the binder, e.g., by adding acompound represented by the general formula (I) having a crosslinkableor polymerizable functional group to the aforementioned coatingcomposition for forming a high refraction film, applying the coatingcomposition to a transparent support, and then subjecting theaforementioned dispersant, polyfunctional monomer or polyfunctionaloligomer and compound represented by the general formula (I) tocrosslinking reaction or polymerization reaction.

A particularly preferred example of the compound represented by thegeneral formula (I) is a compound having (meth)acryloyl group as acrosslinkable or polymerizable functional group, such as3-acryloxylpropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane.

It is also preferred that the binder in the high refraction film have anamino group or quaternary ammonium group. The binder of the highrefraction film having an amino group or quaternary ammonium group canbe formed, e.g., by adding a monomer having a crosslinkable orpolymerizable functional group and an amino group or quaternary ammoniumgroup to the aforementioned coating composition for forming a highrefraction film, applying the coating composition to a transparentsupport, and then subjecting the monomer to crosslinking reaction orpolymerization reaction with the aforementioned dispersant andpolyfunctional monomer or polyfunctional oligomer.

The monomer having an amino group or quaternary ammonium group acts as adispersing medium for the inorganic fine particles in the coatingcomposition. Further, after coating, the monomer can be subjected tocrosslinking reaction or polymerization reaction with the dispersant andpolyfunctional monomer or polyfunctional oligomer to form a binder,making it possible to keep the inorganic fine particles fairly dispersedin the high refraction film and hence prepare a high refraction filmexcellent in physical strength, chemical resistance and weatheringresistance.

Preferred examples of the monomer having an amino group or quaternaryammonium group include N,N-dimethylaminoethyl(meth)acrylate,N,N-dimethylaminopropyl(meth)acrylate, (meth)acrylic acidhydroxypropyltrimethylammonium chloride, dimethylallylammonium chloride,etc.

The amount of the monomer having an amino group or quaternary ammoniumgroup to be used based on the dispersant is preferably from 1 to 40% byweight, more preferably from 3 to 30% by weight, particularly from 3 to20% by weight. By effecting crosslinking or polymerization reaction toform a binder at the same time with or after the coating of the highrefraction film, these monomers are allowed to act effectively beforethe coating of the high refraction film.

The crosslinked or polymerized binder has a structure comprising acrosslinked or polymerized polymer main chain. Examples of the polymermain chain include polyolefin (saturated hydrocarbon), polyether,polyurea, polyurethane, polyester, polyamine, polyamide, and melamineresin. Particularly preferred among these polymer main chains arepolyolefin main chain, polyether main chain and polyurea main chain,more preferably polyolefin main chain and polyether main chain,particularly polyolefin main chain.

The polyolefin main chain is formed by saturated hydrocarbon. Thepolyolefin main chain is obtained, e.g., by addition polymerizationreaction of unsaturated polymerizable group. The polyether main chainhas repeating units bonded to each other with an ether bond (—O—). Thepolyether main chain is obtained, e.g., by the ring-openingpolymerization reaction of an epoxy group. The polyurea main chain hasrepeating units bonded to each other with a urea bond (—NH—CO—NH—). Thepolyurea main chain is obtained, e.g., by the polycondensation reactionof an isocyanate group with an amino group. The polyurethane main chainhas repeating units bonded to each other with a urethane bond(—NH—CO—O—). The polyurethane main chain is obtained, e.g., by thepolycondensation reaction of an isocyanate group with a hydroxyl group(containing N-methylol group). The polyester main chain has repeatingunits connected to each other with an ester bond (—CO—O—). The polyestermain chain is obtained, e.g., by the polycondensation reaction of acarboxyl group (containing an acid halide group) with a hydroxyl group(containing N-methylol group). The polyamine main chain has repeatingunits bonded to each other with an imino bond (—NH—). The polyamine mainchain is obtained, e.g., by the ring-opening polymerization reaction ofethyleneimine group. The polyamide main has repeating units bonded toeach other with an amide bond (—NH—CO—). The polyamide main chain isobtained, e.g., by the reaction of an isocyanate group with a carboxylgroup (containing an acid halide group). The melamine resin main chainis obtained, e.g., by the polycondensation reaction of a triazine group(e.g., melamine) with an aldehyde (e.g., formaldehyde). In the melamineresin, the main chain itself has a crosslinked or polymerized structure.

The anionic group is preferably connected to the main chain as a binderside chain via a connecting group.

Preferred examples of the connecting group for connecting the anionicgroup and the binder main chain to each other include —CO—, —O—,alkylene group, arylene group, and divalent group selected from thegroup consisting of combinations thereof. The crosslinked or polymerizedstructure has two or more main chains chemically bonded (preferablycovalently) to each other. The crosslinked or polymerized structurepreferably has three or more main chains covalently bonded to eachother. The crosslinked or polymerized structure is preferably formed by—CO—, —O—, —S—, nitrogen atom, phosphorus atom, aliphatic residue,aromatic residue and a divalent or higher group selected from the groupconsisting of combinations thereof.

The binder is preferably a copolymer comprising a repeating unit havingan anionic group and a repeating unit having a crosslinked orpolymerizable structure. The proportion of the repeating unit having ananionic group in the copolymer is preferably from 2 to 96 mol %, morepreferably from 4 to 94 mol-%, most preferably from 6 to 92 mol %. Therepeating unit may have two or more anionic groups. The proportion ofthe repeating unit having a crosslinked or polymerized structure in thecopolymer is preferably from 4 to 98 mol %, more preferably from 6 to 96mol %, most preferably from 8 to 94 mol %.

The repeating units in the binder may have both an anionic group and acrosslinked or polymerized structure. The binder may contain otherrepeating units (repeating units free of both anionic group andcrosslinked or polymerized structure).

Preferred examples of the other repeating units include repeating unitscontaining silanol group, amino group or quaternary ammonium group.

In the repeating unit having a silanol group, the silanol group isconnected to the main chain of the binder directly or via a connectinggroup. The silanol group is preferably connected as a side chain to themain chain via a connecting group. Preferred examples of the connectinggroup for connecting the silanol group and the binder main chain to eachother include —CO—, —O—, alkylene group, arylene group, and divalentgroup selected from the group consisting of combinations thereof. Whenthe binder contains a repeating unit having a silanol group, theproportion of the silanol group is preferably from 2 to 98 mol %, morepreferably from 4 to 96 mol %, most preferably from 6 to 94 mol %.

In the repeating unit having an amino group or quaternary ammoniumgroup, the amino group or quaternary ammonium group is connected to themain chain of the binder directly or via a connecting group. The aminogroup or quaternary ammonium group is preferably connected as a sidechain to the main chain via a connecting group. The amino group orquaternary ammonium group is preferably a secondary, tertiary orquaternary ammonium group, more preferably a tertiary or quaternaryammonium group. The group connected to the nitrogen atom in thesecondary, tertiary or quaternary ammonium group is preferably an alkylgroup, more preferably a C₁-C₁₂ alkyl group, even more preferably aC₁-C₆ alkyl group. The counter ion of the quaternary ammonium group ispreferably a halide ion. Preferred examples of the connecting group forconnecting the amino group or quaternary ammonium group and the bindermain chain to each other include —CO—, —NH—, —O—, alkylene group,arylene group, and divalent group selected from the group consisting ofcombinations thereof. When the binder contains a repeating unit havingan amino group or quaternary ammonium group, the proportion of the aminogroup or quaternary ammonium group is preferably from 0.1 to 32 mol %,more preferably from 0.5 to 30 mol %, most preferably from 1 to 28 mol%.

The silanol group and amino group or quaternary ammonium group may becontained in the repeating unit having an anionic group or the repeatingunit having a crosslinked or polymerized structure to exert the sameeffect.

The crosslinked or polymerized binder is preferably formed by applyingthe coating composition for forming a high refraction film to atransparent support, and then subjecting the coating composition tocrosslinking or polymerization reaction at the same time with or aftercoating.

The high refraction film preferably comprises a binder obtained by thecrosslinking or polymerization reaction of an ionizing radiation-curingcompound containing an aromatic ring, an ionizing radiation-curingcompound containing a halogenating element other than fluorine (e.g.,Br, I, Cl), an ionizing radiation-curing compound containing an atomsuch as S, N and P or the like.

The high refraction film may comprise a resin, a surface active agent,an antistat, a coupling agent, a thickening agent, a coloring inhibitor,a coloring material (pigment, dye), an anti-foaming agent, a levelingagent, a fire retardant, an ultraviolet absorber, an infrared absorber,a tackifying agent, a polymerization inhibitor, an oxidation inhibitor,a surface modifier, electrically-conductive metal fine particles, etc.incorporated therein besides the aforementioned components (inorganicfine particles, polymerization initiator, photosensitizer, etc.).

The high refraction film may comprise particles having an averageparticle diameter of from 0.2 to 10 μm as described later incorporatedtherein to act also as ant-glare layer capable of protecting againstglare.

The thickness of the high refraction film can be properties designeddepending on the purpose. In the case where the high refraction film isused as an optical interference layer, the thickness of the highrefraction film is preferably from 30 to 200 nm, more preferably from 50to 170 nm, particularly from 60 to 150 nm. In the case where the highrefraction film acts also as a hard coat layer, the thickness of thehigh refraction film is preferably from 0.5 to 10 μm, more preferablyfrom 1 to 7 μm, particularly from 2 to 5 μm.

In the formation of the high refraction film, the crosslinking reactionor polymerization reaction of the ionizing radiation-curing compound ispreferably effected in an atmosphere having an oxygen concentration ofnot higher than 10% by volume.

By forming the high refraction film in an atmosphere having an oxygenconcentration of not higher than 10% by volume, the physical strength,chemical resistance and weathering resistance of the high refractionfilm and even the adhesiveness of the high refraction film to the layeradjacent thereto can be improved.

More preferably, the high refraction film is formed by the crosslinkingreaction or polymerization reaction of the ionizing radiation-curingcompound in an atmosphere having an oxygen concentration of not higherthan 6% by volume, even more preferably not higher than 4% by volume,particularly not higher than 2% by volume, most preferably not higherthan 1% by volume.

The adjustment of the oxygen concentration to not higher than 10% byvolume is preferably carried out by replacing the atmosphere (nitrogenconcentration: about 79% by volume; oxygen concentration: about 21% byvolume) by other gases, particularly nitrogen (purge with nitrogen).

Preferred examples of coating solvent for the high refraction filminclude methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

The coating solvent may contain solvents other than ketone-basedsolvents. Examples of these solvents include alcohols (e.g., methanol,ethanol, isopropanol, butanol, benzyl alcohol), esters (e.g., methylacetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate,ethyl formate, propyl formate, butylformate), aliphatic hydrocarbons(e.g., hexane, cyclohexane), halogenated hydrocarbons (e.g., methylenechloride, chloroform, carbon tetrachloride), aromatic hydrocarbons(e.g., benzene, toluene, xylene), amides (e.g., dimethylformamide,dimethylacetamide, n-methylpyrrolidone), ethers (e.g., diethyl ether,dioxane, tetrahydrofurane), and ether alcohols (e.g.,1-methoxy-2-propanol).

The content of the ketone-based solvents in the coating solvent ispreferably not lower than 10% by weight, preferably not lower than 30%by weight, more preferably not lower than 60% by weight based on thetotal weight of solvents contained in the coating composition.

The strength of the high refraction film is preferably not lower than H,more preferably not lower than 2H, most preferably not lower than 3Haccording to pencil hardness test of JIS K5400.

The abrasion of the test specimen when subjected to Taber test accordingto JIS K5400 is preferably as small as possible.

The haze of the high refraction film is preferably as low as possible ifit is free of particles providing an anti-glare performance. The haze ofthe high refraction film is preferably not higher than 5%, morepreferably not higher than 3%, particularly not higher than 1%.

Anti-Reflection Film

Further, the anti-reflection film of the present invention also has theaforementioned high refraction film provided on the transparent support.Moreover, the anti-reflection film of the present invention may furtherhave a low refraction film having a lower refractive index than that ofthe high refraction film. The transparent support and various layersprovided in the anti-reflection film of the present invention will bedescribed in detail hereinafter.

Transparent Support

The transparent support is preferably a plastic film. Examples of theplastic film include cellulose esters (e.g., triacetyl cellulose,diacetyl cellulose, propionyl cellulose, butyryl cellulose, acetylpropionyl cellulose, nitrocellulose), polyamides, polycarbonates,polyesters (e.g., polyethylene terephthalate, polyethylene naphthalate,poly-1,4-cyclohexanedimethylene terephthalate,polyethyelene-1,2-diphenoxyethane-4,4′-dicarboxylate,polybutyleneterephthalate), polystyrenes (e.g., syndioctacticpolystyrene), polyolefins (e.g., polypropylene, polyethylene,polymethylpentene), polysulfones, polyethersulfones, polyallylates,polyetherimides, polymethyl methacrylates, and polyether ketones.Preferred among these plastic films are triacetyl cellulose,polycarbonates, polyethyene terephthalates, and polyethylenenaphthalates. In particular, when the product is used for liquid crystaldisplay device, triacetyl cellulose is preferred.

In the case where the transparent support is a triacetyl cellulose film,it is preferably a triacetyl cellulose film prepared by subjecting atriacetyl cellulose dope prepared by dissolving triacetyl cellulose in asolvent to either single-layer casting or multi-layer co-casting.

In particular, from the standpoint of environmental protection, atriacetyl cellulose film prepared from a triacetyl cellulose dopeprepared by subjecting triacetyl cellulose to low temperaturedissolution or high temperature dissolution in a solvent substantiallyfree of dichloromethane is preferred.

The single-layer triacetyl cellulose film is prepared by a drum castingmethod as disclosed in JP-A-7-11055, etc., or a band casting method orthe like while the latter triacetyl cellulose film made of a pluralityof layers is prepared by a so-called co-casting method as disclosed inJP-A-61-94725, JP-B-62-43846, etc.

For example, a solution (dope) obtained by dissolving a raw materialflake in a solvent such as halogenated hydrocarbons (dichloromethane,etc.), alcohols (methanol, ethanol, butanol, etc.), esters (methylformate, methyl acetate, etc.) and ethers (dioxane, tetrahydrofurane,diethylether, etc.), and then optionally adding various additives suchas plasticizer, ultraviolet absorber, deterioration inhibitor, lubricantand peeling accelerator to the solution is cast over a support made of ahorizontal endless metal belt or rotating drum using a dope supplyingunit (referred to as “die”).

In the case of single-layer form, a single dope is subjected tosingle-layer casting. In the case of multi-layer form, a lowconcentration dope and a high concentration dope are subjected toco-casting so that the low concentration dope is laminated on both sidesof the high concentration cellulose ester dope. The dope thus cast isdried on the support to some extent. The film thus rendered rigid ispeeled off the support, and then passed through a drying zone usingvarious conveying units to remove the solvent.

A typical example of the aforementioned solvent for dissolving triacetylcellulose is dichloromethane. However, from the standpoint of globalenvironment or working atmosphere, it is preferred that the solvent besubstantially free of halogenated hydrocarbon such as dichloromethane.The term “substantially free of halogenated hydrocarbon” as used hereinis meant to indicate that the proportion of halogenated hydrocarbon inthe organic solvent falls below 5% by weight (preferably 2% by weight).In the case where a solvent substantially free of dichloromethane isused to prepare the triacetyl cellulose dope, the following specialdissolution method is preferably employed.

A first method is referred to as “cold dissolution method” and will bedescribed hereinafter. Firstly, triacetyl cellulose is gradually addedto a solvent at a temperature around room temperature (−10° C. to 40°C.) with stirring. Subsequently, the mixture is cooled to a temperatureof from −100° C. to −10° C. (preferably from −80° C. to −10° C., morepreferably from −50° C. to −20° C., most preferably from −50° C. to −30°C.). Cooling may be effected over a dry ice-methanol bath (−75° C.) orin a chilled diethylene glycol solution (−30° C. to −20° C.). By thuscooling, the mixture of triacetyl cellulose and solvent is solidified.When the mixture is then heated to a temperature of from 0° C. to 200°C. (preferably from 0° C. to 150° C., more preferably from 0° C. to 120°C., most preferably from 0° C. to 50° C.), a solution having triacetylcellulose fluidized in a solvent is obtained. Heating may be carried outby allowing the mixture to stand at room temperature or heating themixture over a hot bath.

A second method is referred to as “hot dissolution method” and will bedescribed hereinafter. Firstly, triacetyl cellulose is gradually addedto a solvent at a temperature around room temperature (−10° C. to 40°C.) with stirring. The triacetyl cellulose solution of the presentinvention is preferably prepared by adding triacetyl cellulose to amixed solvent containing various solvents so that it is previouslyallowed to swell. In the present method, the dissolved concentration oftriacetyl cellulose is preferably not higher than 30% by weight but ispreferably as high as possible from the standpoint of efficiency indrying during film making. Subsequently, the mixed organic solvent isheated to a temperature of from 70° C. to 240° C. (preferably from 80°C. to 220° C., more preferably from 100° C. to 200° C., most preferablyfrom 100° C. to 190° C.) under a pressure of from 0.2 MPa to 30 MPa. Thesolution thus heated cannot be subjected to coating as it is and thusneeds to be cooled to the lowest boiling point of the solvents used. Inthis case, it is usual to cool the system to a temperature of from −50°C. to 50° C. so that its pressure is returned to ordinary pressure.Cooling may be carried out merely by allowing the high pressure hightemperature container or line in which triacetyl cellulose is receivedto stand at room temperature or preferably by cooling the device with acooling medium such as cooling water.

The thickness of the aforementioned transparent support is notspecifically limited but is preferably from 1 to 300 μm, more preferablyfrom 30 to 150 μm, particularly from 40 to 120 μm, most preferably from40 to 100 μm.

The light transmittance of the transparent support is preferably notlower than 80%, more preferably not lower than 86%. The haze of thetransparent support is preferably not greater than 2.0%, more preferablynot greater than 1.0%. The refractive index of the transparent supportis preferably from 1.4 to 1.7. The transparent support may comprise aninfrared absorber or ultraviolet absorber incorporated therein. Theadded amount of the infrared absorber is preferably from 0.01 to 20% byweight, more preferably from 0.05 to 10% by weight based on the weightof the transparent support. As a lubricant, inert inorganic compoundfine particles may be incorporated in the transparent support. Examplesof the inorganic compound include SiO₂, TiO₂, BaSO₄, CaCO₃, talc, andkaolin.

The transparent support may be subjected to surface treatment. Examplesof surface treatment include chemical treatment, mechanical treatment,corona discharge treatment, flame treating, ultraviolet-lightirradiation, high frequency treatment, glow discharge treatment, activeplasma treatment, laser treatment, mixed acid treatment, and ozoneoxidation. Preferred among these surface treatment methods are glowdischarge treatment, ultraviolet-light irradiation, corona dischargetreatment and flame treating, particularly glow discharge treatment andcorona discharge treatment.

Outermost Layer

An outermost layer mainly composed of fluorine-containing compound ispreferably formed on the anti-reflection film on the high refractionfilm side thereof. The outermost layer mainly composed offluorine-containing compound acts as a low refraction film orstainproofing layer.

The term “mainly composed of fluorine-containing compound” as usedherein is meant to indicate that the content of fluorine-containingcompound in the outermost layer is not lower than 50% by weight,preferably not lower than 60% by weight based on the total weight of theoutermost layer.

The refractive index of the fluorine-containing compound is preferablyfrom 1.35 to 1.50, more preferably from 1.36 to 1.47, even morepreferably from 1.38 to 1.45. Further, the fluorine-containing compoundpreferably contains fluorine atom in an amount of from 35% to 80% byweight, preferably from 45% to 75% by weight.

Examples of the fluorine-containing compound include fluorine-containingpolymer, fluorine-containing silane compound, fluorine-containingsurface active agent, fluorine-containing ether, etc.

Examples of the fluorine-containing polymer include those synthesized bythe crosslinking reaction or polymerization reaction of ethylenicallyunsaturated monomers containing fluorine atom. Examples of theethylenically unsaturated monomers containing fluorine atom includefluoroolefins (e.g., fluoroethylene, vinylidene fluoride,tetrafluoroethylene, hexafluoropropylene,perfluoro-2,2-dimethyl-1,3-dioxol), fluorinated vinylesters, and estersof fluorine-substituted alcohol with acrylic acid or methacrylic acid.

As the fluorine-containing polymer there may be used a copolymercomprising a repeating unit containing fluorine atom and a repeatingunit free of fluorine atom.

The aforementioned copolymer can be obtained by the polymerizationreaction of an ethylenically unsaturated monomer containing fluorineatom with an ethylenically unsaturated monomer free of fluorine atom.

Examples of the ethylenically unsaturated monomer free of fluorine atominclude olefins (e.g., ethylene, propylene, isoprene, vinyl chloride,vinylidene chloride), acrylic acid esters (e.g., methyl acrylate, ethylacrylate, 2-ethylhexyl acrylate), methacrylic acid esters (e.g., methylmethacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycoldimethacrylate), styrenes and derivatives thereof (e.g., styrene,divinylbenzene, vinyltoluene, α-methylstyrene), vinylethers (e.g.,methyl vinyl ether), vinylesters (e.g., vinyl acetate, vinyl propionate,vinyl cinnamate), acrylamides (e.g., N-tert butylacrylamide,N-cyclohexyl acrylamide), methacrylamide, and acrylonitrile.

Examples of the fluorine-containing silane compound include silanecompounds containing perfluoroalkyl group (e.g.,(heptadecafluoro-1,2,2,2-tetradecyl)triethoxysilane).

In the fluorine-containing surface active agent, its hydrophilic moietymay be anionic, cationic, nonionic or amphoteric. The hydrogen atoms inthe hydrocarbon constituting the hydrophobic moiety are partially orentirely substituted by fluorine atom.

The fluorine-containing ether is normally a compound which is used as alubricant. Examples of the fluorine-containing ether includeperfluoropolyethers, etc.

Particularly preferably, the outermost layer is formed by afluorine-containing polymer having a crosslinked or polymerizedstructure incorporated therein. The fluorine-containing polymer having acrosslinked or polymerized structure incorporated therein is obtained bycrosslinking or polymerizing a fluorine-containing polymer having acrosslinkable or polymerizable group.

The fluorine-containing polymer having a crosslinkable or polymerizablegroup can be obtained by incorporating a crosslinkable or polymerizablegroup in a fluorine-containing polymer free of crosslinkable orpolymerizable group as a side chain. The crosslinkable or polymerizablegroup is preferably a functional group which reacts upon the irradiationwith light, preferably ultraviolet ray or electron beam (EB), or heatingto provide the fluorine-containing polymer with a crosslinked orpolymerized structure. Examples of the crosslinkable or polymerizablegroup include groups such as (meth)acryloyl, isocyanate, epoxy,aziridine, oxazoline, aldehyde, carbonyl, hydrazine, carboxyl, methyloland active methylene. As the fluorine-containing polymer having acrosslinkable or polymerizable group there may be used a commerciallyavailable product.

The crosslinking or polymerization reaction of the fluorine-containingpolymer having a crosslinkable or polymerizable group is preferablycarried out by irradiating the coating composition for forming theoutermost layer with light or electron beam or heating the coatingcomposition at the same time with or after the coating of the coatingcomposition.

The outermost layer may contain a filler (e.g., inorganic fineparticles, organic fine particles), a silane coupling agent, a lubricant(silicon compound such as dimethyl silicone, etc.), a surface activeagent, etc. besides the fluorine-containing compound. Particularlypreferably, an inorganic fine particles, a silane coupling agent, and alubricant are incorporated in the outermost layer.

Preferred examples of the inorganic fine particles to be incorporated inthe outermost layer include silicon dioxide(silica), fluorine-containingfine particles (e.g., magnesium fluoride, calcium fluoride, bariumfluoride), etc. Particularly preferred among these inorganic fineparticless is silicon dioxide(silica). The weight-average molecularweight of primary particles constituting the inorganic fine particles ispreferably from 1 to 150 nm, more preferably from 1 to 100 nm, mostpreferably from 1 to 80 nm. In the outermost layer, the inorganic fineparticles are preferably dispersed more finely. The shape of theinorganic fine particles is preferably rice grain-shaped, spherical,cubic, spindle-shaped, short fiber-shaped, ring-shaped or amorphous.

As the silane coupling agent to be incorporated in the outermost layerthere may be used a compound represented by the aforementioned generalformula (I) and/or derivative compound thereof. Preferred examples ofthe silane coupling agent include silane coupling agents containinghydroxyl group, mercapto group, carboxyl group, epoxy group, alkylgroup, alkoxysilyl group, acyloxy group and acylamino group,particularly silane coupling agents containing epoxy group,polymerizable acyloxy group ((meth)acryloyl) and polymerizable acylaminogroup (acrylamino, methacrylamino).

Particularly preferred among the compounds represented by the generalformula (I) is a compound having (meth)acryloyl group as a crosslinkableor polymerizable group such as 3-acryloxypropyltrimethoxysilane and3-methacryloylpropyl trimethoxysilane.

As the lubricant, a fluorine-containing compound having dimethylsiliconor polysiloxane segment incorporated therein is preferred.

The outermost layer is preferably formed by irradiating a coatingcomposition having a fluorine-containing compound and optional arbitrarycomponents dissolved or dispersed therein with light or electron beam orheating the coating composition to cause crosslinking reaction orpolymerization reaction.

In particular, in the case where the outermost layer is formed by thecrosslinking reaction or polymerization reaction of an ionizingradiation-curing compound, the crosslinking reaction or polymerizationreaction is preferably effected in an atmosphere having an oxygenconcentration of not higher than 10% by volume. By forming the outermostlayer in an atmosphere having an oxygen concentration of not higher than10% by volume, an outermost layer excellent in physical strength andchemical resistance can be obtained.

The oxygen concentration is preferably not higher than 6% by volume,more preferably not higher than 4% by volume, particularly not higherthan 2% by volume, most preferably not higher than 1% by volume.

The adjustment of the oxygen concentration to not higher than 10% byvolume is preferably carried out by replacing the atmosphere (nitrogenconcentration: about 79% by volume; oxygen concentration: about 21% byvolume) by other gases, particularly nitrogen (purge with nitrogen).

In the case where the outermost layer is used as a low refraction film,the thickness of the outermost layer is preferably from 30 nm to 200 nm,more preferably from 50 nm to 150 nm, particularly from 60 nm to 120 nm.In the case where the outermost layer is used as a stain-proofing layer,the thickness of the outermost layer is preferably from 3 nm to 50 nm,more preferably from 5 nm to 35 nm, particularly from 7 nm to 25 nm.

The outermost layer preferably exhibits a surface dynamic frictioncoefficient of not greater than 0.25 to improve the physical strength ofthe anti-reflection film. The term “dynamic friction coefficient” asused herein is meant to indicate the dynamic fiction coefficient of thesurface of the outermost layer with respect to a stainless steel spherehaving a diameter of 5 mm measured when the stainless steel sphere isallowed to move along the surface of the outermost layer at a rate of 60cm/min at a load of 0.98 N. The surface dynamic friction coefficient ofthe outermost layer is preferably not greater than 0.17, particularlynot greater than 0.15.

In order to improve the stain-proofness of the anti-reflection film, thecontact angle of the outermost layer with respect to water is preferablynot smaller than 90°, more preferably not smaller than 95°, particularlynot smaller than 100°.

Low Refraction Film

The low refraction film may acts also as the aforementioned outermostlayer or may be disposed under the outermost layer.

In the case where the low refraction film acts also as theaforementioned outermost layer, matters which have bee already describedwith reference to the outermost layer can be applied. In the case wherethe low refraction film is disposed under the outermost layer, the lowrefraction film preferably contains a silicon compound.

The refractive index of the low refraction film is from 1.20 to 1.55,preferably from 1.30 to 1.50, more preferably from 1.35 to 1.48,particularly from 1.40 to 1.48.

In the case where the low refraction film is disposed under theoutermost layer, the low refraction film can be formed by a coatingmethod or gas phase method (vacuum deposition method, sputtering method,ion plating method, plasma CVD method, etc.). The coating method ispreferred because it can produce a low refraction film at a low price.

In the low refraction film is prepared by coating, the low refractionfilm is preferably prepared from a compound selected from the groupconsisting of compound represented by the following general formula(II), hydrolyzate thereof and crosslinked silicon polymer produced bythe condensation of the hydrolyzate, particularly crosslinked siliconpolymer.X_(a)Y_(b)SiZ_(4-a-b)  (II)

In the general formula (II), X represents a C₁-C₁₂ organic group (e.g.,alkyl, aryl, halogenated alkyl, halogenated aryl, alkenyl or epoxygroup, (meth)acryloxy group, mercapto group, amino group, cyano group).Y is a C₁-C₃ hydrocarbon group. Z represents a halogen atom or alkoxygroup (e.g., OCH₃, OC₂H₅, OC₃H₇). The suffixes a and b are the same ordifferent and each are an integer of from 0 to 2. The compound of thegeneral formula (II) is not specifically limited, but specific examplesof the general formula (II) include tetralkoxysilanes such as methylsilicate and ethyl silicate, trialkoxy or triacyloxysilanes such asmethyl trimethoxysilane, methyl triethoxysilane, methyltrimethoxyethoxysilane, methyl triacetoxysilane, methyl tributoxysilane,ethyl trimethoxysilane, vinyl trimethoxysilane, vinyl triethoxysilane,vinyl triacetoxysilane, vinyl trimethoxyethoxysilane, phenyltrimethoxysilane, phenyl triethoxysilane, phenyl triacetoxysilane,γ-chloropropyl trimethoxysilane, γ-chloropropyl triethoxysilane,γ-chloropropyl triacetoxysilane, 3,3,3-trifluoropropyl trimethoxysilane,γ-glycidoxypropyl trimethoxysilane, γ-glycidoxypropyl triethoxysilane,γ-(β-glycidoxyethoxy)propyl trimethoxysilane,β-(3,4-epoxycyclohexyl)ethyl trimethoxysilane,β-(3,4-epoxycyclohexyl)ethyl triethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyl trimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyl trimethoxysilane, γ-mercaptopropyltriethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane,γ-(2-aminoethyl)aminopropyltrimethoxysilane andβ-cyanoethyltriethoxysilane, dialkoxyordiacyloxysilanes such as dimethyldimethoxysilane, dimethyl diethoxysilane, phenylmethyl dimethoxysilane,phenylmethyl diethoxysilane, γ-glycidoxypropylmethyl dimethoxysilane,γ-glycidoxypropylmethyl diethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyl diethoxysilane,γ-chloropropylmethyl dimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyl diacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyl diethoxysilane,γ-mercaptopropylmethyl dimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-aminopropylmethyl dimethoxysilane, γ-aminopropylmethyldiethoxysilane, methyl vinyl dimethoxysilane and methyl vinyldiethoxysilane, etc.

In particular, in the case where hardness is required, silicon compoundscontaining an epoxy group and (meth)acryloyl group are preferred. Thesesilicon compounds maybe used singly or in combination of two or morethereof.

These silicon compounds are preferably cured with various hardeningagents or catalysts. Examples of these hardening agents or catalystsinclude Lewis acid, various acids and bases containing Lewis base, andneutral or basic salts formed thereby, such as organic carboxylic acid,chromic acid, hypochlorous acid, boric acid, bromic acid, seleniousacid, thiosulfuric acid, orthosilicic acid, thiocyanic acid, nitrousacid, aluminic acid, salt of carbonic acid with a metal, particularlyalkaline metal, or ammonium salt of carbonic acid, alkoxide of aluminum,zirconium and titanium and complex compound thereof. In particular,aluminum chelate compounds are preferred. Examples of the aluminumchelate compounds include ethylacetoacetate aluminum diisopropylate,aluminum trisethyl acetoacetate, alkylacetoacetate aluminumdiisopropylate, aluminum monoacetyl acetoacetonate bisethylacetoacetate, aluminum trisacetyl acetate, etc.

The low refraction film preferably comprises an inorganic fineparticles, fine particles such as LiF, MgF₂ and SiO₂, particularly SiO₂,incorporated therein.

The thickness of the low refraction film is preferably from 30 nm to 200nm, more preferably from 50 nm to 150 nm, most preferably from 60 nm to120 nm.

In the case where the low refraction film is free of particles providinganti-glare performance, the haze of the low refraction film ispreferably as low as possible, more preferably not greater than 5%, evenmore preferably not greater than 3%, particularly not greater than 1%.

The strength of the low refraction film is preferably not lower than H,more preferably not lower than 2H, most preferably not lower than 3Haccording to pencil hardness test of JIS K5400.

The abrasion of the test specimen when subjected to Taber test accordingto JIS K5400 is preferably as small as possible.

In the present invention, the low refraction layer is also formed by acured film comprising as a main component a copolymer comprising asessential constituents a repeating unit derived from afluorine-containing vinyl monomer and a repeating unit having a(meth)acryloyl group in its side chain. The term “main component” usedherein means a component having the largest amount (% by mass) incomponents constituting the cured film. The components derived from thecopolymer preferably account for not lower than 70% by weight, morepreferably not lower than 80% by weight, particularly not lower than 90%by weight of the solid content of the film. For the purpose of improvingresistance to scuffing, it is particularly preferable that a hardeningagent such as polyfunctional(meth)acrylatebe further added.

The refractive index of the low refraction layer is preferably from 1.20to 1.49, more preferably from 1.20 to 1.45, particularly from 1.20 to1.44.

The thickness of the low refraction layer is preferably from 50 nm to400 nm, more preferably from 50 nm to 200 nm. The haze of the lowrefraction layer is preferably not greater than 3%, more preferably notgreater than 2%, most preferably not greater than 1%. The particularstrength of the low refraction layer is preferably not lower than H,more preferably not lower than 2H, most preferably not lower than 3Haccording to pencil hardness test at a load of 1 kg.

In order to improve the stain-proofness of the anti-reflection film, thecontact angle of the low refraction layer with respect to water ispreferably not smaller than 90°, more preferably not smaller than 95°,particularly not smaller than 100°.

The copolymer to be used in the low refraction layer of the presentinvention will be described hereinafter.

Examples of the fluorine-containing vinyl monomer include fluoroolefins(e.g., fluoroethylene, vinylidene fluoride, tetrafluoroethylene,hexafluoroethylene, hexafluoropropoylene), partially orfully-fluorinated alkylester derivatives of (meth)acrylic acid (e.g.,Biscoat 6FM (trade name, produced by OSAKA ORGANIC CHEMICAL INDUSTRYLTD.), M-2020 (trade name, produced by DAIKIN INDUSTRIES, LTD.), fullyor partially-fluorinated vinylethers, etc. Preferred among thesefluorine-containing vinyl monomers are perfluoroolefins. Particularlypreferred among these perfluoroolefins is hexafluoropropylene from thestandpoint of refractive index, solubility, transparency, availability,etc. When the composition ratio of these fluorine-containing vinylmonomers is raised, the refractive index of the low refraction layer canbe raised, but the strength of the low refraction layer is reduced. Inthe present invention, the fluorine-containing vinyl monomers arepreferably incorporated in an amount such that the fluorine content inthe copolymer is from 20% to 60% by weight, more preferably from 25% to55% by weight, particularly from 30% to 50% by weight.

The copolymer of the present invention has a repeating unit having a(meth)acryloyl group as an essential constituent in its side chain . Themethod for incorporating a (meth)acryloyl group in the copolymer is notspecifically limited. Examples of such a method include (1) a methodwhich comprises synthesizing a polymer having a nucleophilic group suchas hydroxyl group and amino group, and then allowing (meth)acrylic acidchloride, (meth)acrylic acid anhydride, anhydrous mixture of(meth)acrylic acid and methanesulfonic acid or the like to act on thepolymer, (2) a method which comprises allowing (meth)acrylic acid to acton the aforementioned polymer having a nucleophilic group in thepresence of a catalyst such as sulfuric acid, (3) a method whichcomprises allowing a compound having an isocyanate group such asmethacryloyloxypropyl isocyanate and a (meth)acryloyl group incombination to act on the aforementioned polymer having a nucleophilicgroup, (4) a method which comprises synthesizing a polymer having anepoxy group, and then allowing a (meth)acrylic acid to act on thepolymer, (5) a method which comprises allowing a compound having anepoxy group such as glycidyl methacrylate and a (meth)acrylyol group incombination to act on a polymer having a carboxyl group, (6) a methodwhich comprises polymerizing vinyl monomers having 3-chloropropionicacid ester site, and then subjecting the product to dehydrochlorination,etc. In the present invention, it is particularly preferred that(meth)acryloyl group be incorporated in the polymer having a hydroxylgroup by the method (1) or (2).

When the composition ratio of these repeating units containing(meth)acryloyl group is raised, the strength of the low refraction layercan be enhanced, but the refractive index of the low refraction layer,too, is raised. Though depending on the kind of the repeating unitderived from fluorine-containing vinyl monomer, the repeating unitcontaining (meth)acryloyl group preferably accounts for 5 to 90% byweight, more preferably 30 to 70% by weight, particularly 40 to 60% byweight of the low refraction layer.

The copolymer useful for the present invention may be optionallyobtained by the copolymerization of other vinyl monomers besides theaforementioned repeating unit derived from fluorine-containing vinylmonomer and repeating unit having (meth)acryloyl group in its side chainfrom the standpoint of various views such as adhesiveness to substrate,Tg (contributing to film hardness) of polymer, solubility in solvent,transparency, slipperiness and dust-proofness/stain-proofness. Aplurality of these vinyl monomers may be used in combination dependingon the purpose. These vinyl monomers are preferably incorporated in atotal amount of from 0 to 65 mol %, more preferably from 0 to 40 mol %,particularly from 0 to 30 mol % based on the copolymer.

The vinyl monomer units which can be used in combination with therepeating units are not specifically limited. Examples of these vinylmonomer units include olefins (ethylene, propylene, isoprene, vinylchloride, vinylidene chloride, etc.), acrylic acid esters (methylacrylate, methyl acrylate, ethyl acrylate, 2-ethxylhexyl acrylate,2-hydroxyethyl acrylate), methacrylic acid esters (methyl methacrylate,ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate,etc.), styrene derivatives (styrene, p-hydroxymethylstyrene,p-methoxystyrene), vinylethers (methyl vinyl ether, ethyl vinyl ether,cyclohexyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinylether, etc.), vinyl esters (vinyl acetate, vinyl propionate, vinylcinnamate, etc.), unsaturated carboxylic acids (acrylic acid,methacrylic acid, crotonic acid, maleic acid, itaconic acid, etc.),acrylamides (N,N-dimethylacrylamide, N-tert-butylacrylamide,N-cyclohexylacrylamide, etc.), methacrylamdies(N,N-dimethylmethacrylamide), acrylonitrile, etc.

As a preferred embodiment, the copolymer to be used in the presentinvention is a copolymer of the following general formula (III).

In the general formula (III), L represents a C₁-C₁₀ connecting group,preferably C₁-C₆ connecting group, particularly C₂-C₄ connecting group,which maybe straight-chain or have a branched structure or may have anannular structure or hetero atoms selected from the group consisting ofO, N and S.

Preferred examples of the connecting group include *—(CH₂)₂—O—**,*—(CH₂)₂—NH—**, *—(CH₂)₄—O—**, *—(CH₂)₆—O—**, *—(CH₂)₂—(CH₂)₂—O—**,—CONH—(CH₂)₃—O—**, *—CH₂CH(OH)CH₂—O—*, *—CH₂CH₂OCONH (CH₂)₃—O—** (inwhich * represents a connecting site on the polymer main chain side, and** represents a connecting site on (meth)acryloyl group side),etc. Thesuffix m represents 0 or 1.

In the general formula (III), X represents a hydrogen atom or methylgroup, preferably hydrogen atom from the standpoint of curingreactivity.

In the general formula (III), A represents a repeating unit derived froman arbitrary vinyl monomer. The repeating unit is not specificallylimited so far as it is a constituent of a monomer copolymerizable withhexafluoropropylene and can be properly selected from the standpoint ofvarious views such as adhesiveness to substrate, Tg (contributing tofilm hardness) of polymer, solubility in solvent, transparency,slipperiness and dustproofness/stainproofness. The repeating unit may beformed by a single vinyl monomer or a plurality of vinyl monomersdepending on the purpose.

Preferred examples of the vinyl monomer include vinylethers such asmethyl vinyl ether, ethyl vinyl ether, t-butyl vinyl ether, cyclohexylvinyl ether, isopropyl vinyl ether, hydroxyethyl vinyl ether,hydroxybutyl vinyl ether, glycidyl vinyl ether and allyl vinyl ether,vinyl esters such as vinyl acetate, vinyl propionate and vinyl butyrate,(meth)acrylates such as methyl(meth)acrylate, ethyl(meth)acrylate,hydroxyethyl(meth)acrylate, glycidyl methacrylate, allyl(meth)acrylateand (meth)acryloyloxypropyl trimethoxysilane, styrene derivatives suchas styrene and p-hydroxymethyl styrene, unsaturated carboxylic acidssuch as crotonic acid, maleic acid and itaconic acid, derivativesthereof, etc. Preferred among these vinyl monomers are vinyl etherderivatives and vinyl ester derivatives, particularly vinyl etherderivatives.

The suffixes x, y and z each represent mol % of the respectiveconstituent and represent a value satisfying the relationships 30≦x≦60,5≦y≦70 and 0≦z≦65, preferably 35≦x≦55, 30≦y≦60 and 0≦z≦20, particularly40≦x≦55, 40≦y≦55 and 0≦z≦10, respectively.

A particularly preferred embodiment of the copolymer to be used in thepresent invention is the following general formula (IV).

In the general formula (IV), X, x and y are as defined in the generalformula (III). Preferred ranges of X, x and y are the same as in thegeneral formula (III).

The suffix n represents an integer of from not smaller than 2 to notgreater than 10, preferably from not smaller than 2 to not greater than6, particularly from not smaller than 2 to not greater than 4.

B represents a repeating unit derived from arbitrary vinyl monomer whichmay be a single composition or may be formed by a plurality ofcompositions. Examples of the repeating unit include those describedwith reference to A in the aforementioned general formula (III).

The suffixes z₁ and z₂ each represent mol % of the respectiveconstituent and represent a value satisfying the relationships 0≦z₁≦65and 0≦z₂≦65, preferably, 0≦z₁≦30 and 0≦z₂≦10, particularly 0≦z₁≦10 and0≦z₂≦5, respectively.

The copolymer represented by the general formula (III) or (IV) can besynthesized, e.g., by incorporating a (meth)acryloyl group in acopolymer containing a hexafluoropropylene component and a hydroxyalkylvinyl ether component using any of the afore-mentioned methods.

Preferred examples of copolymers useful in the present invention will begiven below, but the present invention is not limited thereto.

x y m L1 X P-1 50 0 1 *—CH₂CH₂O—** H P-2 50 0 1 *—CH₂CH₂O—** CH₃ P-3 455 1 *—CH₂CH₂O—** H P-4 40 10 1 *—CH₂CH₂O—** H P-5 30 20 1 *—CH₂CH₂O—** HP-6 20 30 1 *—CH₂CH₂O—** H P-7 50 0 0 — H P-8 50 0 1 *—C₄H₈O—** H P-9 500 1 *

 CH₂

₂ O

 CH₂

₂ O—** H P-10 50 0 1

H P-11 50 0 1 *—CH₂CH₂NH—** H P-12 50 0 1

H P-13 50 0 1

CH₃ P-14 50 0 1

CH₃ P-15 50 0 1

H P-16 50 0 1

H P-17 50 0 1

H P-18 50 0 1

CH₃ P-19 50 0 1

CH₃ P-20 40 10 1 *—CH₂CH₂O—** CH₃ The symbol * indicates the polymermain chain side, and the symbol ** indicates (meth)acryloyl group side.

a b b L1 A P-21 55 45 0 *—CH₂CH₂O—** — P-22 45 55 0 *—CH₂CH₂O—** — P-2350 45 5

P-24 50 45 5

P-25 50 45 5

P-26 50 40 10 *—CH₂CH₂O—**

P-27 50 40 10 *—CH₂CH₂O—**

P-28 50 40 10 *—CH₂CH₂O—**

The symbol * indicates the polymer main chain side, and the symbol **indicates acryloyl group side.

x y z1 z2 n X B P-29 50 40 5 5 2 H

P-30 50 35  5 10 2 H

P-31 40 40 10 10 4 CH₃

a b Y Z P-32 45  5

P-33 40 10

x y z Rf L P-34 60 40  0 —CH₂CH₂C₈F_(17—n) —CH₂CH₂O P-35 60 30 10—CH₂CH₂C₄F₈H—n —CH₂CH₂O— P-36 40 60  0 —CH₂CH₂C₆F₁₂H CH₂CH₂CH₂CH₂O—

x y z n Rf P-37 50 50 0 2 —CH₂C₄F₈H—n P-38 40 55 5 2 —CH₂C₄F₈H—n P-39 3070 0 4 —CH₂C₈F₁₇ P-40 60 40 0 2 —CH₂CH₂C₈F₁₆H—n

The synthesis of the copolymer to be used in the present invention canbe carried out by synthesizing a precursor such as hydroxylgroup-containing polymer by any of various polymerization methods suchas solution polymerization, precipitation polymerization, suspensionpolymerization, precipitation polymerization, mass polymerization andemulsion polymerization, and then incorporating a (meth)acryloyl groupin the precursor by the aforementioned polymer reaction. Thepolymerization reaction may be effected by any known method such asbatchwise method, semi-continuous method and continuous method.

Examples of the method for initiating the polymerization include amethod involving the use of a radical polymerization initiator, a methodinvolving irradiation with light or radiation, etc. These polymerizationmethods and polymerization initiating methods are described in TeijiTsuruta, “Kobunshi Gosei Houhou (Polymer Synthesis Method)”, revisededition (published by Nikkan Kogyo Shinbun, 1971) and Takayuki Otsu andMasayoshi Kinoshita, “Koubunshi Gosei no Jikkenho (Method of Experimentof Polymer Synthesis)”, Kagaku Dojin, 1972, pp. 124 to 154.

Particularly preferred among the aforementioned polymerization methodsis solution polymerization method using a radical polymerizationinitiator. As the solvent to be used in solution polymerization theremay be used one or a mixture of two or more of various organic solventssuch as ethyl acetate, butyl acetate, acetone, methyl ethyl ketone,methyl isobutyl ketone, cyclohexanone, tetrahydrofurane, dioxane,N,N-dimethylformamide, N,N-dimethylacetamide, benzene, toluene,acetonitrile, methylene chloride, chloroform, dichloroethane, methanol,ethanol, 1-propanol, 2-propanol and 1-butanol. A mixture of theseorganic solvents with water may be used.

The polymerization temperature needs to be predetermined in connectionwith the molecular weight of the polymer thus produced, the kind of theinitiator, etc. and can range from below 0° C. to above 100° C., but thepolymerization is preferably effected at a temperature of from 50° C. to100° C.

The reaction pressure can be properly predetermined but is normallypreferably from 1 to 100 kg/cm², particularly from 1 to 30 kg/cm². Thereaction time is from about 5 hours to 30 hours.

Preferred examples of the reprecipitation solution for the polymer thusobtained include isopropanol, hexane, methanol, etc.

The low refraction layer-forming composition of the present invention isnormally in liquid form and is prepared by dissolving the aforementionedcopolymer as an essential constituent and optionally various additivesand a radical polymerization initiator in a proper solvent. In thiscase, the solid content concentration is properly predetermineddepending on the purpose but is normally from about 0.01 to 60% byweight, preferably from about 0.5 to 50% by weight, particularly fromabout 1 to 20% by weight.

From the standpoint of improving resistance to scuffing of the lowretraction layer, additives, for example, a hardener such aspolyfunctional (meth)acrylate compound, polyfunctional epoxy compound,polyisocyanate compound, aminoplast, polybasic acid or anhyride thereof,or an inorganic fine particle such as silica, can be added to the lowrefraction layer in a small amount from the standpoint of interfacialadhesiveness to the high refraction layer. The amount of theseadditives, if added, is preferably from 0 to 30% by weight, morepreferably from 0 to 20% by weight, particularly from 0 to 10% by weightbased on the total solid content in the low refraction layer.

For the purpose of providing properties such as stainproofness, waterresistance, chemical resistance and slipperiness, a known silicone-basedor fluorine-based stainproofing agent, a lubricant or the like may beproperly added. The amount of these additives, if added, is preferablyfrom 0 to 20% by weight, more preferably from 0 to 10% by weight,particularly from 0 to 5% by weight based on the total solid content inthe low refraction layer.

Hard Coat Layer

The hard coat layer is provided on the surface of the transparentsupport to provide the anti-reflection film with physical strength. Itis particularly preferred that the hard coat layer be providedinterposed between the transparent support and the aforementioned highrefraction film.

The hard coat layer is preferably formed by the crosslinking reaction orpolymerization reaction of an ionizing radiation-curing compound of lowmolecular weight oligomers or polymers. The hard coat layer can beformed, e.g., by applying a coating composition containing an ionizingradiation-curing polyfunctional monomer or polyfunctional oligomer to atransparent support, and then subjecting the polyfunctional monomer orpolyfunctional monomer or polyfunctional oligomer to crosslinkingreaction or polymerization reaction.

The ionizing radiation-curing polyfunctional monomer or polyfunctionaloligomer is preferably a photopolymerizable, electron ray-polymerizableor radiation-polymerizable functional group, particularlyphotopolymerizable functional group.

Examples of the photopolymerizable functional group include unsaturatedpolymerizable functional groups such as (meth)acryloyl group, vinylgroup, styryl group or allyl group, and cation-polymerizable functionalgroups such as epoxy group, thioepoxy group or vinyl groups. Of those,(meth)acryloyl group and epoxy group are preferable.

Specific examples of the photopolymerizable polyfunctional monomerhaving a photopolymerizable functional group include those exemplifiedwith reference to the high refraction film. The photopolymerizablepolyfunctional monomer is preferably polymerized in the presence of aphotopolymerization initiator or photosensitizer. Thephotopolymerization reaction is preferably carried out by applying ahard coat layer, drying the hard coat layer, and then irradiating thehard coat layer with ultraviolet rays.

The hard coat layer preferably contains an inorganic fine particleshaving an average primary particle diameter of not greater than 200 nm.The term “average particle diameter” as used herein is meant to indicateweight-average diameter. By predetermining the average primary particlediameter to be not greater than 200 nm, a hard coat layer which can keepits desired transparency can be formed.

The inorganic fine particles acts to raise the hardness of the hard coatlayer as well as inhibit the cure shrinkage of the coat layer. Theinorganic fine particles are also added for the purpose of controllingthe refractive index of the hard coat layer.

As the inorganic fine particles there may be used a fine particles ofsilicon dioxide, aluminum oxide, calcium carbonate, barium sulfate,talc, kaolin, calcium sulfate, titanium dioxide, zirconium oxide, tinoxide, ATO, ITO, zinc oxide or the like besides the inorganic fineparticles exemplified with reference to the high refraction film.Preferred among these fine particless are silicon dioxide, titaniumdioxide, zirconium oxide, aluminum oxide, tin oxide, ATO, ITO and zincoxide.

The average primary particle diameter of the inorganic fine particlescontained in the hard coat layer is preferably from 5 nm to 200 nm, morepreferably from 10 nm to 150 nm, even more preferably from 20 nm to 100nm, particularly from 20 nm to 50 nm.

The inorganic fine particles are preferably dispersed in the hard coatlayer as finely as possible.

The particle size of the inorganic fine particles in the hard coat layeris preferably from 5 nm to 300 nm, more preferably from 10 nm to 200 nm,even more preferably from 20 nm to 150 nm, particularly from 20 nm to 80nm as calculated in terms of average particle diameter.

The content of the inorganic fine particles in the hard coat layer ispreferably from 10% to 90% by weight, more preferably from 15% to 80% byweight, particularly from 15% to 75% by weight based on the total weightof the hard coat layer.

As previously mentioned, the high refraction film can act also as a hardcoat layer. In the case where the high refraction film acts also as ahard coat layer, the high refraction film is preferably formed byincorporating inorganic fine particles having a high refractive indexfinely dispersed in the hard coat layer using the method described withreference to the high refraction film.

The hard coat layer may further comprise particles having an averageparticle diameter of from 0.2 μm to 10 μm described later incorporatedtherein to act also as an anti-glare layer having an anti-glareperformance.

The thickness of the hard coat layer can be properly designed dependingon the purpose. The thickness of the hard coat layer is preferably from0.2 μm to 10 μm, more preferably from 0.5 μm to 7 μm, particularly from0.7 μm to 5 μm.

The strength of the hard coat layer is preferably not lower than H, morepreferably not lower than 2H, most preferably not lower than 3Haccording to pencil hardness test of JIS K5400.

The abrasion of the test specimen when subjected to Taber test accordingto JIS K5400 is preferably as small as possible.

In the case where the hard coat layer is formed by the crosslinkingreaction or polymerization reaction of an ionizing radiation-curingcompound, the crosslinking reaction or polymerization reaction ispreferably effected in an atmosphere having an oxygen concentration ofnot greater than 10% by volume. By forming the hard coat layer in anatmosphere having an oxygen concentration of not greater than 10% byvolume, a hard coat layer excellent in physical strength and chemicalresistance can be obtained.

The crosslinking reaction or polymerization reaction is more preferablyeffected in an atmosphere having an oxygen concentration of not greaterthan 6% by volume, even more preferably not greater than 4% by volume,particularly not greater than 2% by volume, most preferably not greaterthan 1% by volume.

The adjustment of the oxygen concentration to not greater than 10% byvolume is preferably carried out by replacing the atmosphere (nitrogenconcentration: about 79% by volume; oxygen concentration: about 21% byvolume) by other gases, particularly nitrogen (purge with nitrogen).

The hard coat layer is preferably formed by applying a coatingcomposition for forming a hard coat layer to the surface of atransparent support.

The coating solvent is preferably a ketone-based solvent as exemplifiedwith reference to the high refraction film. By using such a ketone-basedsolvent, the adhesiveness of the surface of the transparent support(particularly triacetyl cellulose support) to the hard coat layer isfurther improved.

Particularly preferred examples of the coating solvent include methylethyl ketone, methyl isobutyl ketone, and cyclohexanone.

The coating solvent may contain solvents other than the ketone-basedsolvents exemplified with reference to the high refraction film.

Referring to the coating solvent, the content of the ketone-basedsolvent is preferably not smaller than 10% by weight, more preferablynot smaller than 30% by weight, even more preferably 60% by weight basedon the total weight of solvents contained in the coating composition.

Surface Roughness of Anti-Reflection Film

The anti-reflection film to be used in the present invention may haveroughness formed on the surface thereof having the high refraction filmto exhibit anti-glare properties.

The anti-glare properties are related to the average surface roughness(Ra). The surface roughness is preferably from 0.01 μm to 0.4 μm, morepreferably from 0.03 μm to 0.3 μm, even more preferably from 0.05 μm to0.25 μm, particularly from 0.07 μm to 0.2 μm as calculated in terms ofaverage surface roughness (Ra) per surface area of 1 mm2 randomlysampled from area of 100 cm².

The average surface roughness (Ra) is described in Jiro Nara, “HyoumenArasa no Sokutei-Hyoukaho (Method for Measuring and Evaluating SurfaceRoughness)”, Techno Compact Series (6), K. K. Sogo Gijutsu Center.

The shape of valley and mountain on the surface of the anti-reflectionfilm to be used in the present invention can be evaluated by an atomicforce microscope (AFM).

As the method for forming surface roughness there may be used any knownmethod. In the present invention, a method which comprises pressing aplate having a roughened surface against the surface of a film at a highpressure (e.g., embossing) or a method which comprises incorporating afine particles in any layer on the anti-reflection film to form ananti-glare layer, thereby forming roughness on the surface of theanti-reflection film.

As the embossing method for forming roughness on the surface of the filmthere may be used any known method, but it is particularly preferredthat the method described in JP-A-2000-329905 be employed to formroughness.

In the case where a fine particles is incorporated in any layer on theanti-reflection film to form an anti-glare layer, as the fine particlesto be incorporated in the anti-glare layer there is preferably used afine particles having an average particle diameter of from 0.2 μm to 10μm. The term “average particle diameter” as used herein is meant toindicate the weight-average diameter of secondary particles (primaryparticles if particles are not agglomerated).

Examples of the fine particles include inorganic fine particles andorganic fine particles. Specific examples of the inorganic fineparticles include fine particless of silicon dioxide, titanium dioxide,zirconium oxide, aluminum oxide, tin oxide, ITO, zinc oxide, calciumcarbonate, barium sulfate, talc, kaolin, calcium sulfate, etc. Preferredamong these inorganic fine particless are silicon dioxide and aluminumoxide.

As the organic fine particles there is preferably used resin fineparticles. Specific examples of the resin fine particles include fineparticless made of silicon resin, melamine resin, benzoguanamine resin,polymethyl methacrylate resin, polystyrene resin and polyvinylidenefluoride resin. Preferred among these resin fine paticles are those madeof melamine resin, benzoguanamine resin, polymethyl methacrylate resinand polystyrene resin, particularly those made of polymethylmethacrylate resin, benzoguanamine resin and polystyrene resin.

As the fine particles to be used in the anti-glare layer to formroughness there is preferably used resin fine particles.

The average particle diameter of the fine particles is preferably from0.5 μm to 7.0 μm, more preferably from 1.0 μm to 5.0 μm, particularlyfrom 1.5 μm to 4.0 μm.

The refractive index of the fine particles is preferably from 1.35 to1.80, more preferably from 1.40 to 1.75, even more preferably from 1.45to 1.75.

The distribution of particle diameter of the fine particles ispreferably as sharp as possible. S value indicating the distribution ofparticle diameter of the fine particles is represented by the followingequation and is preferably not greater than 2, more preferably notgreater than 1.0, particular not greater than 0.7.S=[D(0.9)−D(0.1)]/D(0.5)

-   -   D(0.1): 10% value of integration of particle diameter calculated        in volume equivalence    -   D(0.5): 50% value of integration of particle diameter calculated        in volume equivalence    -   D(0.9): 90% value of integration of particle diameter calculated        in volume equivalence

The refractive index of the fine particles is not specifically limitedbut is preferably substantially the same (difference of not greater than0.005) as that of the anti-glare layer or different from that of theanti-glare layer by not smaller than 0.02.

By predetermining the refractive index of the fine particles and theanti-glare layer to be substantially the same, the contrast on an imagedisplay device provided with the anti-reflection film is improved.

By making difference in refractive index between the fine particles andthe anti-glare layer, the visibility (glare, angle of view, etc.) of aliquid crystal display provided with the anti-reflection film on thesurface thereof is improved.

In the case where there is provided a difference in refractive indexbetween the fine particles and the anti-glare layer, the difference ispreferably from 0.03 to 0.5, more preferably from 0.03 to 0.4,particularly from 0.05 to 0.3.

The fine particles providing anti-glare performance may be incorporatedin any layer formed on the anti-reflection film, preferably hard coatlayer, low refraction film or high refraction film, particularly hardcoat layer or high refraction film. The fine particles may beincorporated in a plurality of layers.

Other Layers in Anti-Reflection Film

In order to prepare an anti-reflection film having betteranti-reflection performance, a middle refraction layer having arefractive index between that of the high refraction film and that ofthe transparent support is preferably provided.

The middle refraction layer is preferably prepared in the same manner asdescribed with reference to the high refraction film of the presentinvention. The adjustment of the refractive index of the middlerefraction layer can be carried out by controlling the content of theinorganic fine particles in the film.

The anti-reflection film may comprise layers other than mentioned above.For example, an adhesive layer, a shield layer, a sliding layer or anantistatic layer may be provided. The shield layer is provided to shieldelectromagnetic wave or infrared rays.

In the case where the anti-reflection film is applied to a liquidcrystal display device, an undercoat layer having a fine particleshaving an average particle diameter of from 0.1 μm to 10 μm incorporatedtherein may be additionally formed for the purpose of improving theangle of view. The term “average particle diameter” as used herein ismeant to indicate the weight-average particle diameter of secondaryparticles (primary particles if particles are not agglomerated). Theaverage particle diameter of the fine particles is preferably from 0.3μm to 5.0 μm, more preferably from 0.3 μm to 4.0 μm, particularly from0.5 μm to 3.5 μm.

The refractive index of the fine particles is preferably from 1.35 to1.80, more preferably from 1.40 to 1.75, particularly from 1.45 to 1.75.

The distribution of particle diameter of the fine particles ispreferably as sharp as possible. S value indicating the distribution ofparticle diameter of the fine particles is represented by the foregoingequation and is preferably not greater than 1.5, more preferably notgreater than 1.0, particular not greater than 0.7.

The difference in refractive index between the fine particles and theundercoat layer is preferably not smaller than 0.02, more preferablyfrom 0.03 to 0.5, even more preferably from 0.05 to 0.4, particularlyfrom 0.07 to 0.3.

Examples of the fine particles to be incorporated in the undercoat layerinclude the inorganic fine particles and organic fine particlesdescribed with reference to the anti-glare layer.

The undercoat layer is preferably formed interposed between the hardcoat layer and the transparent support. The undercoat layer can act alsoas a hard coat layer.

In the case where the undercoat layer comprises a fine particles havingan average particle diameter of from 0.1 μm to 10 μm incorporatedtherein, the haze of the undercoat layer is preferably from 3% to 60%,more preferably from 5% to 50%, even more preferably from 7% to 45%,particularly from 10% to 40%.

Method for Forming Anti-Reflection Film, etc.

In the present invention, the various layers constituting theanti-reflection film are preferably prepared by a coating method. In thecase where the various layers are formed by a coating method, dipcoating method, air knife coating method, curtain coating method, rollercoating method, wire bar coating method, gravure coating method, microgravure coating method or extrusion coating method (described in U.S.Pat. No. 2,681,294) may be employed. Two or more layers may be coatedsimultaneously. The simultaneous coating method is described in U.S.Pat. Nos. 2,761,791, 2,941,898, 3,508,947 and 3,526,528, and YujiHarasaki, “Kotingu Kogaku (Coating Engineering)”, Asakura Shoten, page253, 1973. Wire bar coating method, gravure coating method and microgravure coating method are preferred.

The various layer in the anti-reflection film may comprise a resin, asurface active agent, an antistat, a coupling agent, a thickening agent,a coloring inhibitor, a coloring material (pigment, dye), ananti-foaming agent, a leveling agent, a fire retardant, an ultravioletabsorber, a tackifying agent, a polymerization inhibitor, an oxidationinhibitor, a surface modifier, etc. incorporated therein besides theaforementioned fine particles, polymerization initiator andphotosensitizer.

In the present invention, the anti-reflection film preferably exhibits adynamic friction coefficient of not greater than 0.25 on the highrefraction layer side thereof to improve the physical strength (scratchresistance, etc.) thereof. The term “dynamic friction coefficient” asused herein is meant to indicate the dynamic fiction coefficient of thesurface of the high refraction film side with respect to a stainlesssteel sphere having a diameter of 5 mm measured when the stainless steelsphere is allowed to move along the surface of the high refraction filmside at a rate of 60 cm/min at a load of 0.98 N. The surface dynamicfriction coefficient of the high refraction film side is preferably notgreater than 0.17, particularly not greater than 0.15.

The anti-reflection film preferably exhibits a contact angle of notsmaller than 90°, more preferably not smaller than 95°, particularly not100° with respect to water on the high refraction film side thereof toimprove its anti-glare properties.

In the case where the anti-reflection film has no anti-glareperformance, the haze of the anti-reflection film is preferably as lowas possible.

In the case where the anti-reflection film has an anti-glareperformance, the haze of the anti-reflection film is preferably from0.5% to 50%, more preferably from 1% to 40%, most preferably from 1% to30%.

Constitution of Anti-Reflection Film

Examples of the constitution of the anti-reflection film of the presentinvention will be described in connection with the drawings.

FIG. 1 is a schematic sectional view illustrating typically the layerstructure of an anti-reflection film having an excellent anti-reflectionperformance.

The embodiment shown in FIG. 1( a) has a layer structure having atransparent support 1, a hard coat layer 2, a high refraction film 3 anda low refraction film (outermost layer) 4 disposed in this order. Thetransparent support 1, the high refraction film 3 and the low refractionfilm 4 each have a refractive index satisfying the followingrelationship. Refractive index of high refraction film>refractive indexof transparent support>refractive index of low refraction film

The layer structure shown in FIG. 1( a) is advantageous in that when thehigh refraction film and the low refraction film satisfy the followingequations (1) and (2), respectively, an anti-reflection film having abetter anti-reflection performance can be prepared as described inJP-A-59-50401.(mλ/4)×0.7<n ₁ d ₁<(mλ/4)×1.3  (1)

In the equation (1), m represents a positive integer (normally 1, 2 or3), n₁ represents the refractive index of the high refraction film, andd₁ represents the thickness (nm) of the high refraction film. λrepresents the wavelength of visible light ranging from 380 to 680 (nm).(nλ/4)×0.7<n ₂ d ₂<(nλ/4)×1.3  (2)

In the equation (2), n represents a positive odd number (normally 1), n₂represents the refractive index of the low refraction film, and d₂represents the thickness (nm) of the low refraction film. λ representsthe wavelength of visible light ranging from 380 to 680 (nm).

The term “satisfying the equations (1) and (2)” as used herein is meantto indicate that there are m (positive integer which is normally 1, 2 or3) satisfying the equation (1) and n (odd number which is normally 1)satisfying the equation (2) within the aforementioned range ofwavelength. This can apply to the following equations (3) to (8).

The embodiment shown in FIG. 1( b) has a layer structure having atransparent support 1, a hard coat layer 2, a middle refraction layer 5,a high refraction film 3 and a low refraction film (outermost layer) 4provided in this order. The transparent support 1, hard coat layer 2,middle refraction layer 5, high refraction film 3 and low refractionfilm 4 each have a refractive index satisfying the followingrelationship.

Refractive index of high refraction film>refractive index of middlerefraction layer>refractive index of transparent support>refractiveindex of low refraction film

The layer structure shown in FIG. 1( b) is advantageous in that when themiddle refraction film, the high refraction film and the low refractionfilm satisfy the following equations (3), (4) and (5), respectively, ananti-reflection film having a better anti-reflection performance can beprepared as described in JP-A-59-50401.(hλ/4)×0.7<n ₃ d ₃<(hλ/4)×1.3  (3)

In the equation (3), h represents a positive integer (normally 1, 2 or3), n₃ represents the refractive index of the middle refraction film,and d₃ represents the thickness (nm) of the middle refraction film. λrepresents the wavelength of visible light ranging from 380 to 680 (nm).(iλ/4)×0.7<n ₄ d ₄<(iλ/4)×1.3  (4)

In the equation (4), i represents a positive integer (normally 1, 2 or3), n₄ represents the refractive index of the high refraction film, andd₄ represents the thickness (nm) of the high refraction film. λrepresents the wavelength of visible light ranging from 380 to 680 (nm).(jλ/4)×0.7<n ₅ d ₅<(jλ/4)×1.3  (5)

In the equation (5), j represents a positive odd number (normally 1), n₅represents the refractive index of the low refraction film, and d₅represents the thickness (nm) of the low refraction film. λ representsthe wavelength of visible light ranging from 380 to 680 (nm).

In the layer structure shown in FIG. 1( b), it is particularly preferredthat the middle refraction layer, the high refraction film and the lowrefraction film satisfy the following equations (6), (7) and (8),respectively.

Herein, λ is 500 nm, h is 1, i is 2, and j is 1.(hλ/4)×0.80<n ₃ d ₃<(hλ/4)×1.00  (6)(iλ/4)×0.75<n ₄ d ₄<(iλ/4)×0.95  (7)(jλ/4)×0.95<n ₅ d ₅<(jλ/4)×1.05  (8)

The term “high refractive index, middle refractive index, low refractiveindex” as used herein is meant to indicate the magnitude of therefractive index of the layers relative to each other. In FIGS. 1( a)and (b), the high refraction film is used as an optical interferencelayer, making it possible to prepare an anti-reflection film having anextremely excellent anti-reflection performance.

It is also preferred that the hard coat layer, middle refraction layeror middle refraction film comprise a fine particles having an averageparticle diameter of from 0.2 μm to 10 μm incorporated therein toprepare an anti-glare film having an anti-glare performance.

The embodiment shown in FIG. 2( a) has a layer structure having atransparent support 1, anti-glare layer (high refraction film) 6 and alow refraction film (outermost layer) 4 provided in this order. The fineparticles 7 incorporated in the anti-glare layer are fine particleshaving an average particle diameter of from 0.2 μm to 10 μm.

The embodiment shown in FIG. 2( b) has a layer structure having atransparent support 1, a hard coat layer 2, an anti-glare layer (highrefraction film) 6 and a low refraction film (outermost layer) 4provided in this order. The fine particles 7 incorporated in theanti-glare layer 6 is a fine particles having an average particlediameter of from 0.2 μm to 10 μm.

In the embodiments shown in FIGS. 2( a) and (b), the transparent support1, the anti-glare layer (high refraction film) 6 and the low refractionfilm 4 each have a refractive index satisfying the followingrelationship.

Refractive index of anti-glare layer>refractive index of transparentsupport>refractive index of low refraction film The layer structuresshown in FIGS. 2( a) and (b) are advantageous in that when the lowrefraction film 4 satisfies the following equation (9), an excellentanti-reflection film can be prepared.(kλ/4)×0.7<n ₆ d ₆<(kλ/4)×1.3  (9)

In the equation (9), k represents a positive odd number (normally 1), n₆represents the refractive index of the low refraction film, and d₆represents the thickness (nm) of the low refraction film. λ representsthe wavelength of visible light ranging from 380 to 680 (nm).

The term “satisfying the equation (9)” as used herein is meant toindicate that there is k (positive odd number which is normally 1)satisfying the equation (9) within the aforementioned range ofwavelength.

The embodiments shown in FIGS. 2( a) and (b) are preferably used whenthe high refraction film is provided with hard coat properties, makingit possible to prepare an anti-reflection film having an extremelyexcellent physical strength (scratch resistance, etc.).

Polarizing Plate

The polarizing plate of the present invention has an anti-reflectionfilm of the present invention provided on at least one side of aprotective film (protective film for polarizing plate) for polarizingfilm. The protective film for polarizing plate preferably exhibits acontact angle of not greater than 40° with respect to water on thesurface of the transparent support on the side thereof opposite the highrefraction film, i.e., on the side thereof to be laminated with thepolarizing film as mentioned above.

By using the anti-reflection film of the present invention as aprotective film for polarizing plate, a polarizing plate having ananti-reflection performance can be prepared, making it possible todrastically reduce the cost and the thickness of display device.

Further, by preparing a polarizing plate having an anti-reflection filmof the present invention provided on one side of the protective film forpolarizing plate and an optically anisotropic optically-compensated filmprovided on the other side of the protective film for polarizing plate,a polarizing plate can be prepared which can improve the daylightcontrast of liquid crystal display device and drastically raise thehorizontal and vertical angle of view.

Polarizing Film

As the polarizing film to be used in the polarizing plate of the presentinvention there may be used any known material. The polymer film to beused in the polarizing film is not specifically limited and may be afilm made of a proper thermoplastic polymer soluble in volatilesolvents. Examples of the polymer include PVA, polycarbonate, celluloseacylate, polysulfone, etc. The method for stretching the polymer film isnot specifically limited. Any known stretching method may be employed.

Protective Film for Polarizing Plate

In the case where the anti-reflection film of the present invention isused as a protective film for polarizing film (protective film forpolarizing plate), the anti-reflection film preferably exhibits acontact angle of not greater than 40°, more preferably not greater than30°, particularly not greater than 25° with respect to water on thesurface of the transparent support on the side thereof opposite the highrefraction film, i.e., on the side thereof to be laminated with thepolarizing film.

When the contact angle is not greater than 40°, it is useful to improvethe adhesiveness to a polarizing plate mainly composed of polyvinylalcohol.

As the transparent support there is particularly preferably used atriacetyl cellulose film.

Examples of the method for preparing the protective film for polarizingplate of the present invention include the following two methods.

(1) Method which comprises applying the aforementioned various layers(e.g., high refraction film, hard coat layer, outermost layer) to oneside of a saponified transparent support.

(2) Method which comprises applying the aforementioned various layers(e.g., high refraction film, hard coat layer, low refraction film,outermost layer) to one side of a transparent support, and thensubjecting the coated material to saponification on the side thereof tobe laminated with the polarizing film.

In the method (1), when only one side of the transparent support hasbeen saponified, the various layers are applied to the transparentsupport on the unsaponified side thereof. When the transparent supporthas been saponified on both sides thereof, the transparent support isthen subjected to surface treatment such as corona discharge treatment,glow discharge treatment and flame treating on the saponified sidethereof to be coated with the various layers before the application ofthe various layers.

In the method (2), the anti-reflection film is preferably entirelydipped in a saponifying solution. In this case, the anti-reflection filmmay be dipped in a saponifying solution with the side having the variouslayers protected by a protective film so that the transparent support issubjected to saponification on the side thereof to be laminated with thepolarizing film.

Alternatively, the anti-reflection film may be coated with a saponifyingsolution on the surface of the transparent support on the side thereofto be laminated with the polarizing film so that the transparent supportis subjected to saponification on the side thereof to be laminated withthe polarizing film.

The method (2) is advantageous in that a protective film for polarizingplate can be produced at a low price.

The protective film for polarizing plate is required to satisfy opticalproperties (anti-reflection performance, anti-glare performance),physical properties (scratch resistance, etc.), chemical resistance,stainproofness (stain resistance, etc.) and weathering resistance(resistance to moist heat, light-resistance) as defined with referenceto the anti-reflection film of the present invention.

Accordingly, the protective film for polarizing plate preferablyexhibits a dynamic friction coefficient of not greater than 0.25, morepreferably not greater than 0.17, particularly not greater than 0.15 onthe side thereof having a high refraction film.

Further, the protective film for polarizing plate preferably exhibits acontact angle of not lower than 90°, more preferably not lower than 95°,not lower than 100° with respect to water on the side thereof having ahigh refraction film.

Saponification

The aforementioned saponification is preferably carried out by any knownmethod, e.g., dipping the transparent support or anti-reflection film inan alkaline solution for a proper period of time.

The alkaline solution is preferably an aqueous solution of sodiumhydroxide. The concentration of the aqueous solution of sodium hydroxideis preferably from 0.5 to 3 N, particularly from 1 to 2 N. Thetemperature of the alkaline solution is preferably from 30° C. to 70°C., particularly from 40° C. to 60° C.

The transparent support or anti-reflection film which has thus beendipped in the alkaline solution is preferably thoroughly washed withwater or dipped in a diluted acid to neutralize the alkaline componentso that prevent the alkaline component from remaining in the film.

When saponification is effected, the surface of the transparent supportis hydrophilized. The protective film for polarizing plate is bonded toa polarizing film on the hydrophilized surface of the transparentsupport.

The hydrophilized surface is useful to improve the adhesiveness of thetransparent support to a polarizing film mainly composed of polyvinylalcohol.

The saponification is preferably effected in such a manner that thecontact angle of the transparent support with respect to water on theside thereof opposite the high refraction film is not greater than 40°,more preferably not greater than 30°, particularly not greater than 25°.

Optically Compensated Film

The optically compensated film (retardation film) can improve the angleof view of a liquid crystal display.

As the optically compensated film there may be used any known material.For the purpose of raising the angle of view, however, an opticallycompensated sheet as described in U.S. Pat. Nos. 2,587,396 and2,565,644, JP-A-2002-82226 may be used. Particularly preferred is anoptically compensated film having an optically anisotropic layer formedby a compound having a discotic structural unit provided on atransparent support which changes in the angle between the surface of adisc of the discotic compound and the support with the distance from thetransparent support as described in JP-A-2001-100042. In other words,the compound having a discotic structural unit may be hybrid-oriented,bent-oriented, twist-oriented, homogeneously-oriented,homeotropically-oriented or otherwise oriented, particularlyhybrid-oriented.

The angle preferably increases with the rise of the distance from thesupport side of the optically anisotropic layer.

In the case where the optically compensated film is used as a protectivefilm for polarizing film, the optically compensated film is preferablysaponified on the side thereof to be laminated with the polarizing film.The saponification is preferably effected according to theaforementioned saponification method.

Also preferred are an embodiment wherein the transparent support is acellulose ester, an embodiment wherein an oriented layer is formedinterposed between the optically compensated film and the transparentsupport, an embodiment wherein the transparent support has an opticallynegative uniaxiality and an optic axis extending in the direction ofline normal to the surface of the transparent support, an embodimenthaving an optical biaxiality and an embodiment satisfying the followingconditions.20≦{(n _(x) +n _(y))/2−n _(z) }×d≦400wherein n_(x) represents the in-plane refractive index in the directionof retarded axis (maximum in-plane refractive index); n_(y) representsthe in-plane refractive index in the direction perpendicular to retardedaxis; n_(z) represents the refractive index in the directionperpendicular to the plane; and d represents the thickness (nm) of theoptically anisotropic layer.Image Display Device

The anti-reflection film can be applied to an image display device suchas liquid crystal display device (LCD), plasma display panel (PDP),electroluminescence display and cathode ray tube display device (CRT).The anti-reflection film is bonded to an image display device in such anarrangement that the transparent support side of the anti-reflectionfilm is opposed to the image display surface of the image displaydevice.

FIGS. 3 and 4 each are a schematic sectional view illustrating typicallyvarious embodiments wherein the anti-reflection film of the presentinvention is applied to an image display device.

FIG. 3( a) illustrates a preferred embodiment wherein an anti-reflectionfilm is applied to an image display device, particularly PDP, ELD orCRT. The anti-reflection film has a transparent support (1) bonded tothe image display surface of the image display device with an adhesivelayer (8) interposed therebetween.

FIG. 3( b) and FIGS. 4( a) and 4(b) each are a preferred embodimentwherein an anti-reflection film is applied to LCD. In FIG. 3( b), thetransparent support (1) of the anti-reflection film is bonded to aprotective film (9) of a polarizing film with an adhesive layer (8)interposed therebetween. The other protective film (10) of thepolarizing plate is bonded to the liquid crystal display surface of aliquid crystal display device with an adhesive layer (8) interposedtherebetween.

In FIG. 4( a), the transparent support (1) of the anti-reflection film(protective film for polarizing plate) is bonded to a polarizing film(11) with an adhesive layer (8) interposed therebetween. A protectivefilm (10) of the polarizing film is bonded to the liquid crystal displaysurface of a liquid crystal display device with an adhesive layer (8)interposed therebetween. In FIG. 4( b), the anti-reflection film(protective film for polarizing plate) of the present invention has atransparent support (1) bonded directly to a polarizing film (11). Aprotective film (10) of the polarizing film is bonded to the liquidcrystal display surface of a liquid crystal display device with anadhesive layer (8) interposed therebetween. The adhesive layer (8) maycomprise additives such as fine particles and dye incorporated therein.

The anti-reflection film and polarizing plate to be used in the presentinvention can be used in a transmission type, reflection type orsemi-transmission type liquid crystal display device in a mode such astwisted nematic (TN) mode, supertwisted nematic (STN), verticalalignment (VA) mode, in-plane switching (IPS) mode and opticallycompensated bend cell (OCB) mode.

In the case where the anti-reflection film or polarizing plate is usedin a transmission or semi-transmission type liquid crystal displaydevice, it can be used in combination with a commercially availablebrightness enhancement film (polarization separation film having apolarization selection layer such as D-BEF, produced by Sumitomo 3M) toobtain a display device having a higher visibility.

Further, the anti-reflection film or polarizing plate can be combinedwith a λ/4 plate to form a polarizing plate for reflection type liquidcrystal or surface protective plate for organic EL display whicheliminates reflected light from the surface and interior thereof.

EXAMPLES

The present invention will be further described in the followingexamples, but the scope of the present invention should not beinterpreted only by these examples.

Example 1-1

Preparation of Coating Solution for Hard Coat Layer

To 315.0 g of a mixture of dipentaerythritol pentaacrylate anddipentaerythritol hexaacrylate (DPHA, produced by NIPPON KAYAKU CO.,LTD.) were added 450.0 g of a methyl ethyl ketone dispersion of silicafine particles (MEK-ST, solid content concentration: 30% by weight,produced by NISSAN CHEMICAL INDUSTRIES, LTD.), 15.0 g of methyl ethylketone, 220.0 g of cyclohexanone and 16.0 g of a photopolymerizationinitiator (Irgacure 907, produced by Cibasophy Ciba-Geigy JapanLimited). The mixture was then stirred. The mixture was then filteredthrough a filter made of polypropylene having a pore diameter of 0.4 μmto prepare a coating solution for hard coat layer. Preparation ofdispersion of titanium dioxide fine particles

Cobalt-containing titanium dioxide fine particles (MPT-129, produced byISHIHARA SANGYO KAISHA, LTD.) which had not been subjected to surfacetreatment (surface treatment with aluminum hydroxide and zirconiumhydroxide) was prepared.

To 257.1 g of the aforementioned fine particles were then added 38.6 gof the following dispersant and 704.3 g of cyclohexanone. The mixturewas then subjected to dispersion using a dynomill to prepare adispersion of titanium dioxide having a weight-average diameter of 70nm.

Preparation of Coating Solution for Middle Refraction Layer

To 88.9 g of the above dispersion of titanium dioxide were added 58.4 gof a mixture of dipentaerythritol pentaacrylate and dipentaerythritolhexaacrylate (DPHA, produced by NIPPON KAYAKU CO., LTD.), 3.1 g of aphotopolymerization initiator (Irgacure 907, produced by CibasophyCiba-Geigy Japan Limited), 1.1 g of a photosensitizer (Kayacure DETX,produced by NIPPON KAYAKU CO., LTD.), 482.4 g of methyl ethyl ketone and1,869.8 g of cyclohexanone. The mixture was then stirred. The mixturewas then filtered through a filter made of polypropylene having a porediameter of 0.4 μm to prepare a coating solution for middle refractionlayer.

Preparation of Coating Solution for High Refraction Layer

To 586.8 g of the aforementioned dispersion of titanium dioxide wereadded 49.9 g of a mixture of dipentaerythritol pentaacrylate anddipentaerythritol hexaacrylate (DPHA, produced by NIPPON KAYAKU CO.,LTD.), 4.0 g of a photopolymerization initiator (Irgacure 907, producedby Cibasophy Ciba-Geigy Japan Limited), 1.3 g of a photosensitizer(Kayacure DETX, produced by NIPPON KAYAKU CO., LTD.), 455.8 g of methylethyl ketone and 1,427.8 g of cyclohexanone. The mixture was thenstirred. The mixture was then filtered through a filter made ofpolypropylene having a pore diameter of 0.4 μm to prepare a coatingsolution for high refraction layer.

Preparation of Silane Compound

In a reaction vessel equipped with an agitator and a reflux condenserwere charged and mixed 161 parts by weight of3-acryloxypropyltrimethoxysilane (KBM-5103, produced by Shin-EtsuChemical Co., Ltd.), 123 parts by weight of oxalic acid and 415 parts byweight of ethanol. The mixture was reacted at 70° C. for 4 hours, andthen cooled to room temperature to obtain a transparent silane compoundas a curable composition. The silane compound thus obtained had aweight-average molecular weight of 1,600, and the components having amolecular weight of from 1,000 to 20,000 account for 100% of theoligomer or higher components. The gas chromatography of the silanecompound showed that 3-acryloxypropyltrimethoxysilane as a startingmaterial had not been left therein.

Preparation of Coating Solution for Low Refraction Film

A heat crosslinkable fluorine-containing polymer having a refractiveindex of 1.42 (Opstar JN7228; solid content concentration: 6% by weight,produced by JSR Corporation) was subjected to solvent substitution toobtain a methyl isobutyl ketone solution of heat crosslinkable fluorinepolymer having a solid content concentration of 10% by weight. To 56.0 gof the aforementioned heat crosslinkable fluorine polymer solution werethen added 8.0 g of a methyl ethyl ketone dispersion of silica fineparticles (MEK-ST, solid content concentration: 30% by weight, producedby NISSAN CHEMICAL INDUSTRIES, LTD.), 1.75 g of the aforementionedsilane compound, 73.0 g of methyl isobutyl ketone and 33.0 g ofcyclohexanone. The mixture was then stirred. The mixture was thenfiltered through a filter made of polypropylene having a pore diameterof 0.4 μm to prepare a coating solution for low refraction layer.

Preparation of Anti-Reflection Film

The coating solution for hard coat layer was applied to a triacetylcellulose film having a thickness of 80 μm (TD-80UF, produced by FujiPhoto Film Co., Ltd.) using a gravure coater. The coated material wasdried at 100° C., and then irradiated with ultraviolet ray having anilluminance of 400 mW/cm² from a 160 W/cm air-cooled metal halide lamp(produced by EYGRAPHICS CO., LTD.) at a dose of 300 mJ/cm² while the airin the reaction vessel was being purged with nitrogen to an oxygenconcentration of not greater than 1.0% by volume to cause the coat layerto be cured, thereby forming a hard coat layer having a thickness of 3.5μm.

The coating solution for middle refraction layer was applied to thehardcoat layer using a gravure coater. The coated material was dried at100° C., and then irradiated with ultraviolet ray having an illuminanceof 550 mW/cm² from a 240 W/cm air-cooled metal halide lamp (produced byEYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm² while the air in thereaction vessel was being purged with nitrogen to an oxygenconcentration of not greater than 1.0% by volume to cause the coat layerto be cured, thereby forming a middle refraction layer (refractiveindex: 1.65; thickness: 67 nm).

The coating solution for high refraction layer was then applied to themiddle refraction layer using a gravure coater. The coated material wasdried at 100° C., and then irradiated with ultraviolet ray having anilluminance of 550 mW/cm² from a 240 W/cm air-cooled metal halide lamp(produced by EYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm² while the airin the reaction vessel was being purged with nitrogen to an oxygenconcentration of not greater than 1.0% by volume to cause the coat layerto be cured, thereby forming a high refraction layer (refractive index:1.93; thickness: 107 nm).

The coating solution for low refraction layer was then applied to thehigh refraction layer using a gravure coater. The coated material wasdried at 80° C., irradiated with ultraviolet ray having an illuminanceof 550 mW/cm² from a 240 W/cm air-cooled metal halide lamp (produced byEYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm² while the air in thereaction vessel was being purged with nitrogen to an oxygenconcentration of not greater than 1.0% by volume, and then heated to120° C. for 10 minutes to form a low refraction layer (refractive index:1.43; thickness: 86 nm). Thus, an anti-reflection film was prepared.

Comparative Example 1-A

Preparation of Anti-Reflection Film

An anti-reflection film was prepared in the same manner as in Example1-1 except that titanium dioxide fine particle (TTO-55N, produced byISHIHARA SANGYO KAISHA, LTD.) were used instead of the cobalt-containingtitanium dioxide fine particles of Example 1-1. The high refractionlayer had a refractive index of 1.93 and a thickness of 107 nm.

Example 1-2

Preparation of Titanium Dioxide Fine Particles

Cobalt-containing titanium dioxide fine particles doped with cobalttherein were prepared according to a known method for the preparation oftitanium dioxide fine particles and a known doping method(JP-A-5-330825) except that iron (Fe) was replaced by cobalt.

The doped amount of cobalt was 98.5/1.5 as calculated in terms of Ti/Co(by weight).

The titanium dioxide fine particles thus prepared were recognized tohave a rutile type crystal structure and had an average primary particlesize of 40 nm and a specific surface area of 44 m²/g.

Preparation of Anti-Reflection Film

An anti-reflection film was prepared in the same manner as in Example1-1 except that the titanium dioxide fine particles prepared above wasused instead of the cobalt-containing titanium dioxide fine particles ofExample 1-1. The high refraction layer had a refractive index of 1.93and a thickness of 107 nm.

Example 1-3

Preparation of Titanium Dioxide Fine Particles

Aluminum-containing titanium dioxide fine particles doped with aluminumtherein were prepared according to a known method for the preparation oftitanium dioxide fine particles and a known doping method(JP-A-5-330825) except that iron (Fe) was replaced by aluminum. Thedoped amount of aluminum was 97.5/2.5 as calculated in terms of Ti/Al(by weight).

The titanium dioxide fine particles thus prepared were recognized tohave a rutile type crystal structure and had an average primary particlesize of 39 nm and a specific surface area of 43 m²/g.

Preparation of Anti-Reflection Film

An anti-reflection film was prepared in the same manner as in Example1-1 except that the titanium dioxide fine particles prepared above wereused instead of the cobalt-containing titanium dioxide fine particles ofExample 1-1. The high refraction layer had a refractive index of 1.92and a thickness of 107 nm.

Example 1-4

Preparation of Titanium Dioxide Fine Particles

Zirconium-containing titanium dioxide fine particles doped withzirconium therein were prepared according to a known method for thepreparation of titanium dioxide fine particles and a known doping method(JP-A-5-330825) except that iron (Fe) was replaced by zirconium. Thedoped amount of zirconium was 97.5/2.5 as calculated in terms of Ti/Zr(by weight).

The titanium dioxide fine particles thus prepared were recognized tohave a rutile type crystal structure and had an average primary particlesize of 40 nm and a specific surface area of 39 m²/g.

Preparation of Anti-Reflection Film

An anti-reflection film was prepared in the same manner as in Example1-1 except that the titanium dioxide fine particles prepared above wereused instead of the cobalt-containing titanium dioxide fine particles ofExample 1-1. The high refraction layer had a refractive index of 1.92and a thickness of 107 nm.

Example 1-5

Preparation of Titanium Dioxide Fine Particles

Cobalt/aluminum-containing titanium dioxide fine particles doped withcobalt and aluminum therein were prepared according to a known methodfor the preparation of titanium dioxide fine particles and a knowndoping method (JP-A-5-330825) except that iron (Fe) was replaced bycobalt and aluminum. The doped amount of cobalt and aluminum was97.5/1.25/1.25 as calculated in terms of Ti/Co/Al (by weight).

The titanium dioxide fine particles thus prepared were recognized tohave a rutile type crystal structure and had an average primary particlesize of 40 nm and a specific surface area of 39 m²/g.

Preparation of Anti-Reflection Film

An anti-reflection film was prepared in the same manner as in Example1-1 except that the titanium dioxide fine particles prepared above wereused instead of the cobalt-containing titanium dioxide fine particles ofExample 1-1. The high refraction layer had a refractive index of 1.92and a thickness of 107 nm.

Comparative Example 1-B

Preparation of Titanium Dioxide Fine Particles

Titanium dioxide fine particles were prepared in the same manner as inExample 1-2 except that there were no doping elements.

The titanium dioxide fine particles thus prepared were recognized tohave a rutile type crystal structure and had an average primary particlesize of 39 nm and a specific surface area of 42 m²/g.

Preparation of Anti-Reflection Film

An anti-reflection film was prepared in the same manner as in Example1-1 except that the titanium dioxide fine particles prepared above wereused instead of the cobalt-containing titanium dioxide fine particles ofExample 1-1. The high refraction layer had a refractive index of 1.93and a thickness of 107 nm.

Evaluation of Anti-Reflection Film

The anti-reflection films thus prepared (Examples 1-1 to 1-5,Comparative Examples 1-A and 1-B) were then evaluated for the followingproperties. The results are shown in Table 1.

(1) Evaluation of Haze

The anti-reflection film was evaluated for haze using a haze meter(NHD-1001DP, produced by Nippon Denshoku Industries Co., Ltd.).

(2) Evaluation of Reflectance

The spectral reflectance at an incidence angle of 5° was measured at awavelength of from 380 nm to 780 nm using a spectrophotometer (V-550,ARV-474, produced by JASCO Corporation). The average reflectance at awavelength of from 450 nm to 650 nm was then determined.

(3) Evaluation of Weathering Resistance

Using a xenon arc lamp type light-resistance testing machine (XF type),a weathering resistance test was effected with light transmitted by aquartz filter in an atmosphere of a temperature of 63° C. and a relativehumidity of 50% at an exposure time of 0 hour, 300 hours, 600 hours and900 hours.

The anti-reflection film which had been thus exposed was thenmoisture-conditioned at a temperature of 25° C. and a relative humidityof 60% for 2 hours.

The anti-reflection film was then given a checkerboard cut comprising 11longitudinal lines and 11 crosswise lines, totaling 100 squares, by acutter knife on the surface thereof having a high refraction layer, andthen subjected to adhesion test with a polyester adhesive tape (No. 31B)produced by NIITO DENKO CORPORATION three times on the same site. Theanti-reflection film was then observed for the occurrence of peeling.The results were then evaluated according to the following 4-stepcriterion.

-   -   No checkers observed peeled out of 100 checkers: E    -   2 or less checkers observed peeled out of 100 checkers: G    -   3 to 10 checkers observed peeled out of 100 checkers: F    -   More than 10 checkers observed peeled out of 100 checkers: P

TABLE 1 Average Haze reflectance Weathering resistance (%) (%) 0 hr 300hr 600 hr 900 hr Example 1-1 0.35 0.34 E E E E Comparative 0.38 0.35 E FP P Example 1-A Example 1-2 0.33 0.32 E E E E Example 1-3 0.36 0.33 E EG F Example 1-4 0.35 0.33 E E G F Example 1-5 0.34 0.34 E E E EComparative 0.34 0.34 E F P P Example 1-B

Example 2-1

Preparation of Coating Solution for Hard Coat Layer

To 315.0 g of a mixture of dipentaerythritol pentaacrylate anddipentaerythritol hexaacrylate (DPHA, produced by NIPPON KAYAKU CO.,LTD.) were added 450.0 g of a methyl ethyl ketone dispersion of silicafine particles (MEK-ST, solid content concentration: 30% by weight,produced by NISSAN CHEMICAL INDUSTRIES, LTD.), 15.0 g of methyl ethylketone, 220.0 g of cyclohexanone and 16.0 g of a photopolymerizationinitiator (Irgacure 907, produced by Cibasophy Ciba-Geigy JapanLimited). The mixture was then stirred. The mixture was then filteredthrough a filter made of polypropylene having a pore diameter of 0.4 μmto prepare a coating solution for hard coat layer. Preparation ofdispersion of titanium dioxide fine particles

Cobalt-containing titanium dioxide fine particles (MPT-129, produced byISHIHARA SANGYO KAISHA, LTD.) which had not been subjected to surfacetreatment (surface treatment with aluminum hydroxide and zirconiumhydroxide) were prepared.

To 257.1 g of the aforementioned fine particles were then added 38.6 gof the following dispersant, an additive(N,N-dimethylaminoethylacrylate) and 701.7 g of cyclohexanone. Themixture was then subjected to dispersion using a dynomill to prepare adispersion of titanium dioxide having a weight-average diameter of 70nm.

Preparation of Coating Solution for Middle Refraction Layer

To 88.9 g of the aforementioned dispersion of titanium dioxide wereadded 58.4 g of a mixture of dipentaerythritol pentaacrylate anddipentaerythritol hexaacrylate (DPHA, produced by NIPPON KAYAKU CO.,LTD.), 3.1 g of a photopolymerization initiator (Irgacure 907, producedby Cibasophy Ciba-Geigy Japan Limited), 1.1 g of a photosensitizer(Kayacure DETX, produced by NIPPON KAYAKU CO., LTD.), 482.4 g of methylethyl ketone and 1,869.8 g of cyclohexanone. The mixture was thenstirred. The mixture was then filtered through a filter made ofpolypropylene having a pore diameter of 0.4 μm to prepare a coatingsolution for middle refraction layer.

Preparation of Coating Solution for High Refraction Layer

To 586.8 g of the aforementioned dispersion of titanium dioxide wereadded 49.9 g of a mixture of dipentaerythritol pentaacrylate anddipentaerythritol hexaacrylate (DPHA, produced by NIPPON KAYAKU CO.,LTD.), 4.0 g of a photopolymerization initiator (Irgacure 907, producedby Cibasophy Ciba-Geigy Japan Limited), 1.3 g of a photosensitizer(Kayacure DETX, produced by NIPPON KAYAKU CO., LTD.), 455.8 g of methylethyl ketone and 1,427.8 g of cyclohexanone. The mixture was thenstirred. The mixture was then filtered through a filter made ofpolypropylene having a pore diameter of 0.4 μm to prepare a coatingsolution for high refraction layer.

Preparation of Silane Compound

In a reaction vessel equipped with an agitator and a reflux condenserwere charged and mixed 161 parts by weight of3-acryloxypropyltrimethoxysilane (KBM-5103, produced by Shin-EtsuChemical Co., Ltd.), 123 parts by weight of oxalic acid and 415 parts byweight of ethanol. The mixture was reacted at 70° C. for 4 hours, andthen cooled to room temperature to obtain a transparent silane compoundas a curable composition. The silane compound thus obtained had aweight-average molecular weight of 1,600, and the components having amolecular weight of from 1,000 to 20,000 account for 100% of theoligomer or higher components. The gas chromatography of the silanecompound showed that 3-acryloxypropyltrimethoxysilane as a startingmaterial had not been left therein.

Preparation of Coating Solution for Low Refraction Layer

A heat crosslinkable fluorine-containing polymer having a refractiveindex of 1.42 (Opstar JN7228; solid content concentration: 6% by weight,produced by JSR Corporation) was subjected to solvent substitution toobtain a methyl isobutyl ketone solution of heat crosslinkable fluorinepolymer having a solid content concentration of 10% by weight. To 56.0 gof the aforementioned heat crosslinkable fluorine polymer solution werethen added 8.0 g of a methyl ethyl ketone dispersion of silica fineparticles (MEK-ST, solid content concentration: 30% by weight, producedby NISSAN CHEMICAL INDUSTRIES, LTD.), 1.75 g of the aforementionedsilane compound, 73.0 g of methyl isobutyl ketone and 33.0 g ofcyclohexanone. The mixture was then stirred. The mixture was thenfiltered through a filter made of polypropylene having a pore diameterof 0.4 μm to prepare a coating solution for low refraction layer.

Preparation of Anti-Reflection Film

The coating solution for hard coat layer was applied to a triacetylcellulose film having a thickness of 80 μm (TD-80UF, produced by FujiPhoto Film Co., Ltd.) using a gravure coater. The coated material wasdried at 100° C., and then irradiated with ultraviolet ray having anilluminance of 400 mW/cm² from a 160 W/cm air-cooled metal halide lamp(produced by EYGRAPHICS CO., LTD.) at a dose of 300 mJ/cm² while the airin the reaction vessel was being purged with nitrogen to an oxygenconcentration of not greater than 1.0% by volume to cause the coat layerto be cured, thereby forming a hard coat layer having a thickness of 3.5μm.

The coating solution for middle refraction layer was applied to thehardcoat layer using a gravure coater. The coated material was dried at100° C., and then irradiated with ultraviolet ray having an illuminanceof 550 mW/cm² from a 240 W/cm air-cooled metal halide lamp (produced byEYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm² while the air in thereaction vessel was being purged with nitrogen to an oxygenconcentration of not greater than 1.0% by volume to cause the coat layerto be cured, thereby forming a middle refraction layer (refractiveindex: 1.65; thickness: 67 nm).

The coating solution for high refraction layer was then applied to themiddle refraction layer using a gravure coater. The coated material wasdried at 100° C., and then irradiated with ultraviolet ray having anilluminance of 550 mW/cm² from a 160 W/cm air-cooled metal halide lamp(produced by EYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm² while the airin the reaction vessel was being purged with nitrogen to an oxygenconcentration of not greater than 1.0% by volume to cause the coat layerto be cured thereby forming a high refraction layer (refractive index:1.93; thickness: 107 nm).

The coating solution for low refraction layer was then applied to thehigh refraction layer using a gravure coater. The coated material wasdried at 80° C., irradiated with ultraviolet ray having an illuminanceof 550 mW/cm² from a 240 W/cm air-cooled metal halide lamp (produced byEYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm² while the air in thereaction vessel was being purged with nitrogen to an oxygenconcentration of not greater than 1.0% by volume, and then heated to120° C. for 10 minutes to form a low refraction layer (refractive index:1.43; thickness: 86 nm). Thus, an anti-reflection film was prepared.

Comparative Example 2-A

Preparation of Anti-Reflection Film

An anti-reflection film was prepared in the same manner as in Example2-1 except that titanium dioxide fine particles (TTO-55N, produced byISHIHARA SANGYO KAISHA, LTD.) were used instead of the cobalt-containingtitanium dioxide fine particles of Example 2-1. The high refractionlayer had a refractive index of 1.93 and a thickness of 107 nm.

Example 2-2

Preparation of Anti-Reflection Film

An anti-reflection film was prepared in the same manner as in Example2-1 except that the cobalt-doped titanium dioxide fine particlesprepared in Example 1-2 were used instead of the cobalt-containingtitanium dioxide fine particles of Example 2-1. The high refractionlayer had a refractive index of 1.93 and a thickness of 107 nm.

Example 2-3

Preparation of Anti-Reflection Film

An anti-reflection film was prepared in the same manner as in Example2-1 except that the aluminum-doped titanium dioxide fine particlesprepared in Example 1-3 were used instead of the cobalt-containingtitanium dioxide fine particles of Example 2-1. The high refractionlayer had a refractive index of 1.92 and a thickness of 107 nm.

Example 2-4

Preparation of Anti-Reflection Film

An anti-reflection film was prepared in the same manner as in Example2-1 except that the zirconium-doped titanium dioxide fine particlesprepared in Example 1-4 was used instead of the cobalt-containingtitanium dioxide fine particles of Example 2-1. The high refractionlayer had a refractive index of 1.92 and a thickness of 107 nm.

Example 2-5

Preparation of Anti-Reflection Film

An anti-reflection film was prepared in the same manner as in Example2-1 except that the cobalt/aluminum-doped titanium dioxide fineparticles prepared in Example 1-5 were used instead of thecobalt-containing titanium dioxide fine particles of Example 2-1. Thehigh refraction layer had a refractive index of 1.92 and a thickness of107 nm.

Comparative Example 2-B

Preparation of Anti-Reflection Film

An anti-reflection film was prepared in the same manner as in Example2-1 except that the titanium dioxide fine particles prepared inComparative Example 1-B was used instead of the cobalt-containingtitanium dioxide fine particles of Example 2-1. The high refractionlayer had a refractive index of 1.93 and a thickness of 107 nm.

Evaluation of Anti-Reflection Film

The anti-reflection films thus prepared (Examples 2-1 to 2-5,Comparative Examples 2-A and 2-B) were then evaluated in the same manneras in Example 1. The results are shown in Table 2.

TABLE 2 Average Haze reflectance Weathering resistance (%) (%) 0 hr 300hr 600 hr 900 hr Example 2-1 0.32 0.33 E E E E Comparative 0.35 0.36 E FP P Example 2-A Example 2-2 0.31 0.33 E E E E Example 2-3 0.35 0.35 E EG F Example 2-4 0.34 0.34 E E G F Example 2-5 0.32 0.34 E E E EComparative 0.33 0.36 E F P P Example 2-B

Example 3

Evaluation of Image Display Device

The anti-reflection films of the present invention prepared in Examples1-1 to 1-5 and 2-1 to 2-5 were each attached to the display surface ofan image display device to prepare image display devices. The imagedisplay devices comprising the anti-reflection films of the presentinvention exhibited an excellent anti-reflection performance and hencean extremely excellent visibility.

Example 4

Preparation of Protective Film for Polarizing Plate

A saponifying solution was prepared by keeping a 1.5 N aqueous solutionof sodium hydroxide at 50° C. Further, a 0.01 N aqueous solution ofdiluted sulfuric acid was prepared.

The anti-reflection films prepared in Examples 1-1 to 1-5 and Examples2-1 to 2-5 were each subjected to saponification with the aforementionedsaponifying solution on the surface of the transparent support on theside thereof opposite the side having the high refraction layer of thepresent invention.

The transparent support which had been saponified was thoroughly washedwith water to remove the aqueous solution of sodium hydroxide therefrom,washed with the aforementioned diluted aqueous solution of sulfuricacid, thoroughly washed with water to remove the diluted aqueoussolution of sulfuric acid, and then thoroughly dried at 100° C.

The anti-reflection film was then evaluated for contact angle withrespect to water on the saponified surface of the transparent support onthe side thereof opposite the side having the high refraction layer. Thecontact angle was not greater than 40 degrees. Thus, a protective filmfor polarizing plate was prepared.

Preparation of Polarizing Plate

A polyvinyl alcohol film having a thickness of 75 μm (produced byKURARAY CO., LTD.) was dipped in an aqueous solution comprising 100parts by weight of water, 7 parts by weight of iodine and 105 parts byweight of potassium iodide so that iodine was adsorbed thereto.Subsequently, this film was longitudinally monoaxially stretched by afactor of 4.4 in a 4 wt % aqueous solution of boric acid, and then driedwhile being tensed to prepare a polarizing plate.

The anti-reflection film (protective film for polarizing plate) of thepresent invention was then adhered to one side of the polarizing platewith a polyvinyl alcohol-based adhesive as an adhesive in such anarrangement that the saponified triacetyl cellulose side thereof wasopposed to the polarizing plate. Further, a triacetyl cellulose filmwhich had been saponified in the same manner as mentioned above wasadhered to the other side of the polarizing plate with the samepolyvinyl alcohol-based adhesive.

Evaluation of Image Display Device

TN, STN, IPS, VA and OCB mode transmission type, reflection type orsemi-transmission type liquid crystal display devices provided with thepolarizing plate of the present invention thus prepared exhibited anexcellent anti-reflection performance and hence an extremely excellentvisibility.

Example 5

Preparation of Polarizing Plate

An optically anisotropic optically-compensated film having a disc ofdiscotic structural unit disposed oblique to the surface of thetransparent support which changes in its angle between the disc ofdiscotic structural unit and the surface of the transparent support withthe distance from the transparent support (Wide View Film SA-12B,produced by Fuji Photo Film Co., Ltd.) was subjected to saponificationon the side thereof opposite the side having an optically anisotropiclayer under the same conditions as in Example 4.

The anti-reflection film (protective film for polarizing plate) preparedin Example 4 was then adhered to one side of the polarizing filmprepared in Example 4 with a polyvinyl alcohol-based adhesive as anadhesive in such an arrangement that the saponified triacetyl celluloseside thereof was opposed to the polarizing film. Further, the saponifiedoptically compensated film was adhered to the other side of thepolarizing film with the same polyvinyl alcohol-based adhesive in suchan arrangement that the triacetyl cellulose side thereof was opposed tothe polarizing film.

Evaluation of Image Display Device

TN, STN, IPS, VA and OCB mode transmission type, reflection type orsemi-transmission type liquid crystal display devices provided with thepolarizing plate of the present invention thus prepared exhibited anexcellent contrast, a very wide vertical and horizontal angle of view,an excellent anti-reflection performance and an extremely excellentvisibility and display quality as compared with liquid crystal displaydevices provided with a polarizing plate free of optically compensatedfilm.

Example 6-1

Preparation of Coating Solution for Hard Coat Layer

To 315.0 g of a mixture of dipentaerythritol pentaacrylate anddipentaerythritol hexaacrylate (DPHA, produced by NIPPON KAYAKU CO.,LTD.) were added 450.0 g of a methyl ethyl ketone dispersion of silicafine particles (MEK-ST, solid content concentration: 30% by weight,produced by NISSAN CHEMICAL INDUSTRIES, LTD.), 15.0 g of methyl ethylketone, 220.0 g of cyclohexanone and 16.0 g of a photopolymerizationinitiator (Irgacure 907, produced by Cibasophy Ciba-Geigy JapanLimited). The mixture was then stirred. The mixture was then filteredthrough a filter made of polypropylene having a pore diameter of 0.4 μmto prepare a coating solution for hard coat layer. Preparation ofdispersion of titanium dioxide fine particles

To 250 g of titanium dioxide fine particles (TTO-55B, produced byISHIHARA SANGYO KAISHA, LTD.) were added 37.5 g of the followingdispersant, 2.5 g of a cationic monomer (DMAEA, produced by KOHJIN Co.,Ltd.) and 710 g of cyclohexanone. The mixture was then subjected todispersion using a dynomill to prepare a dispersion of titanium dioxidehaving a weight-average diameter of 65 nm.

Preparation of Coating Solution for Middle Refraction Layer

To 155.2 g of the aforementioned dispersion of titanium dioxide wereadded 89.5 g of a mixture of dipentaerythritol pentaacrylate anddipentaerythritol hexaacrylate (DPHA, produced by NIPPON KAYAKU CO.,LTD.), 4.68 g of a photopolymerization initiator (Irgacure 907, producedby Cibasophy Ciba-Geigy Japan Limited), 1.56 g of a photosensitizer(Kayacure DETX, produced by NIPPON KAYAKU CO., LTD.), 770.4 g of methylethyl ketone and 2,983.0 g of cyclohexanone. The mixture was thenstirred. The mixture was then filtered through a filter made ofpolypropylene having a pore diameter of 0.4 μm to prepare a coatingsolution for middle refraction layer.

Preparation of Coating Solution for High Refraction Layer

To 985.7 g of the aforementioned dispersion of titanium dioxide wereadded 48.8 g of a mixture of dipentaerythritol pentaacrylate anddipentaerythritol hexaacrylate (DPHA, produced by NIPPON KAYAKU CO.,LTD.), 33.5 g of an acrylic group-containing silane coupling agent(KBM-5103, produced by Shin-Etsu Chemical Co., Ltd.), 4.03 g of aphotopolymerization initiator (Irgacure 907, produced by CibasophyCiba-Geigy Japan Limited), 1.35 g of a photosensitizer (Kayacure DETX,produced by NIPPON KAYAKU CO., LTD.), 622.5 g of methyl ethyl ketone and1,865.0 g of cyclohexanone. The mixture was then stirred. The mixturewas then filtered through a filter made of polypropylene having a porediameter of 0.4 μm to prepare a coating solution for high refractionlayer.

Preparation of Coating Solution for Low Refraction Layer

To 93.0 g of a heat crosslinkable fluorine-containing polymer having arefractive index of 1.42 (Opstar JN7228; solid content concentration: 6%by weight, produced by JSR Corporation) were added 8.0 g of a methylethyl ketone dispersion of silica fine particles (MEK-ST, solid contentconcentration: 30% by weight, produced by NISSAN CHEMICAL INDUSTRIES,LTD.), 8.0 g of an acryloyl group-containing silane coupling agent(KBM-5103, produced by Shin-Etsu Chemical Co., Ltd.), 100.0 g of methylethyl ketone, and 5.0 g of cyclohexanone. The mixture was then stirred.The mixture was then filtered through a filter made of polypropylenehaving a pore diameter of 1 μm to prepare a coating solution for lowrefraction layer.

Preparation of Anti-Reflection Film

The coating solution for hard coat layer was applied to a triacetylcellulose film having a thickness of 80 μm (TD-80UF, produced by FujiPhoto Film Co., Ltd.) using a gravure coater. The coated material wasdried at 100° C., and then irradiated with ultraviolet ray having anilluminance of 400 mW/cm² from a 160 W/cm air-cooled metal halide lamp(produced by EYGRAPHICS CO., LTD.) at a dose of 300 mJ/cm²while the airin the reaction vessel was being purged with nitrogen to an oxygenconcentration of not greater than 1.0% by volume to cause the coat layerto be cured, thereby forming a hard coat layer having a thickness of 3.5μm.

The coating solution for middle refraction layer was applied to the hardcoat layer using a gravure coater. The coated material was dried at 100°C., and then irradiated with ultraviolet ray having an illuminance of550 mW/cm² from a 240 W/cm air-cooled metal halide lamp (produced byEYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm² while the air in thereaction vessel was being purged with nitrogen to an oxygenconcentration of not greater than 1.0% by volume to cause the coat layerto be cured, thereby forming a middle refraction layer (refractiveindex: 1.63; thickness: 67 nm).

The coating solution for high refraction layer was then applied to themiddle refraction layer using a gravure coater. The coated material wasdried at 100° C., and then irradiated with ultraviolet ray having anilluminance of 550 mW/cm² from a 240 W/cm air-cooled metal halide lamp(produced by EYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm² while the airin the reaction vessel was being purged with nitrogen to an oxygenconcentration of not greater than 1.0% by volume to cause the coat layerto be cured, thereby forming a high refraction layer (refractive index:1.90; thickness: 107 nm).

The coating solution for low refraction layer was then applied to thehigh refraction layer using a gravure coater. The coated material wasdried at 80° C., irradiated with ultraviolet ray having an illuminanceof 550 mW/cm² from a 240 W/cm air-cooled metal halide lamp (produced byEYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm² while the air in thereaction vessel was being purged with nitrogen to an oxygenconcentration of not greater than 1.0% by volume, and then heated to120° C. for 10 minutes to form a low refraction layer (refractive index:1.43; thickness: 86 nm). Thus, an anti-reflection film was prepared. Inthe middle refraction layer and high refraction layer, the dispersantwas crosslinked and/or polymerized with the binder by the aforementionedirradiation with light.

Evaluation of Anti-Reflection Film

The anti-reflection films thus prepared were then evaluated for thefollowing properties. The results are shown in Table 3.

(1) Evaluation of Resistance to Scratch with Steel Wool

The surface of the anti-reflection film on the side thereof having ahigh refraction layer was observed for scratch developed when a #0000steel wool was allowed to make two reciprocal movements over the surfaceof the anti-reflection film at a load of 1.96 N/cm². The results werethen evaluated to the following four-step criterion.

-   E: No scratch observed-   G: Some substantially invisible scratches observed-   F: Definitely visible scratches observed-   P: Definitely visible scratches observed remarkably    (2) Evaluation of Pencil Hardness

The anti-reflection film was moist-conditioned at a temperature of 25°C. and a relative humidity of 60% for 2 hours. The anti-reflection filmwas then evaluated for pencil hardness on the surface thereof having ahigh refraction layer with a testing pencil defined in JIS S6006according to the pencil hardness evaluation method defined in JIS K5400.The load was 4.9 N.

(3) Evaluation of Dynamic Friction Coefficient

The anti-reflection film was evaluated for dynamic friction coefficienton the side thereof having a high refraction layer as an index ofsurface slipperiness. For the measurement of dynamic frictioncoefficient, the sample was moist-conditioned at a temperature of 25° C.and a relative humidity of 60% for 2 hours. Using a dynamic frictionmeasuring instrument (HEIDON-14) with a stainless steel sphere having adiameter of 5 mm, measurement was effected at a load of 0.98 N and arate of 60 cm/min.

(4) Evaluation of Chemical Resistance

Methyl ethyl ketone was dropped onto the surface of the anti-reflectionfilm on the side thereof having a high refraction layer. Methyl ethylketone was then wiped away with a cleaning cloth. The anti-reflectionfilm was then observed for film exfoliation. The results were thenevaluated according to the following 2-step criterion.

-   -   G: No film exfoliation    -   P: Film exfoliation        (5) Evaluation of Finger Print Wipability

The anti-reflection film was finger-printed on the side thereof having ahigh refraction layer. The finger-printed surface of the anti-reflectionfilm was then wiped with a cleaning cloth. The anti-reflection film wasthen observed. The results were then evaluated according to thefollowing 3-step criterion.

-   -   G: Finger print fully wiped away    -   F: Finger print partially left unwiped    -   P: Finger print substantially fully left unwiped        (6) Evaluation of Magic Ink Wipability

The anti-reflection film was stained with an oil-based magic ink (ZEBRAMacky, red) on the side thereof having a high refraction layer, and thenallowed to stand for 1 minute. The oil-based magic ink was then wipedoff with a cleaning cloth. The anti-reflection film was then observed.The results were then evaluated according to the following 3-stepcriterion.

-   -   G: Magic ink fully wiped away    -   F: Magic ink partially left unwiped    -   P: Magic ink substantially fully left unwiped        (7) Evaluation of Contact Angle

The anti-reflection film was moist-conditioned at a temperature of 25°C. and a relative humidity of 60% for 2 hours. The anti-reflection filmwas then evaluated for contact angle with water on the side thereofhaving a high refraction layer.

(8) Evaluation of Checkerboard Adhesion

The anti-reflection film was moist-conditioned at a temperature of 25°C. and a relative humidity of 60% for 2 hours. The anti-reflection filmwas then given a checkerboard cut comprising 11 longitudinal lines and11 crosswise lines, totaling 100 squares, by a cutter knife on thesurface thereof having a high refraction layer, and then subjected toadhesion test with a polyester adhesive tape (No. 31B) produced by NIITODENKO CORPORATION three times on the same site. The anti-reflection filmwas then observed for the occurrence of peeling. The results were thenevaluated according to the following 4-step criterion.

-   -   E: No checkers observed peeled out of 100 checkers    -   G: 2 or less checkers observed peeled out of 100 checkers    -   F: 3 to 10 checkers observed peeled out of 100 checkers    -   P: More than 10 checkers observed peeled out of 100 checkers        (9) Evaluation of Light-Resistance

Using a xenon arc lamp type light-resistance testing machine (XF type),a light-resistance test was effected with light transmitted by a quartzfilter in an atmosphere of a temperature of 63° C. and a relativehumidity of 50% at an exposure time of 100 hours, 200 hours and 300hours.

The anti-reflection film which had been thus exposed was thenmoisture-conditioned at a temperature of 25° C. and a relative humidityof 60% for 2 hours.

The anti-reflection film was then given a checkerboard cut comprising 11longitudinal lines and 11 crosswise lines, totaling 100 squares, by acutter knife on the surface thereof having a high refraction layer, andthen subjected to adhesion test with a polyester adhesive tape (No. 31B)produced by NIITO DENKO CORPORATION three times on the same site. Theanti-reflection film was then observed for the occurrence of peeling.The results were then evaluated according to the following 4-stepcriterion.

-   -   E: No checkers observed peeled out of 100 checkers    -   G: 2 or less checkers observed peeled out of 100 checkers    -   F: 3 to 10 checkers observed peeled out of 100 checkers    -   P: More than 10 checkers observed peeled out of 100 checkers

TABLE 3 Resistance to Dynamic Finger Magic Checker- Anti- scratch Pencilfirction print ink Contact board glare with steel hard- coef- Chemicalwipa- wipa- angle adhesive- Ra perfor- Light-resistance wool nessficient ressitance biity bility (°) ness (μm) mance 100 hr 200 hr 300 hrExample 6-1 E 3H 0.10 G G G 104 E — — E G F Example 6-2 E 3H 0.10 G G G103 E — — E G F Example 6-3 F 3H 0.09 G G G 103 E — — E G F Example 6-4G 3H 0.23 G G G 101 E — — E G F Example 6-5 E 3H 0.11 G G G 102 E 0.06 GE G F Example 6-6 E 3H 0.11 G G G 102 E 0.06 G E G F Example 6-7 E 3H0.10 G G G 102 E — — E G F Example 6-8 G 3H 0.09 G G G 103 E — — E G FExample 6-9 E 3H 0.11 G G G 102 E — — E G F Example 6-10 E 3H 0.10 G G G102 E — — E G F Example 6-11 E 3H 0.12 G G G 101 E 0.07 G E G F Example6-12 E 3H 0.12 G G G 103 E 0.06 G E G F Example 6-13 E 3H 0.10 G G G 104E — — E G F Example 6-14 G 3H 0.09 G G G 103 E — — E G F Example 6-15 E3H 0.10 G G G 102 E — — E G F Example 6-16 E 3H 0.09 G G G 103 E — — E GF Example 6-17 E 3H 0.11 G G G 104 E — — E G F Example 6-18 E 3H 0.10 GG G 103 E — — E G F Example 6-19 E 3H 0.10 G G G 102 E — — E G F Example6-20 E 3H 0.11 G G G 104 E — — E G F Example 6-21 E 3H 0.11 G G G 103 E0.13 E E G F Example 6-22 G 3H 0.11 G G G 103 E 0.13 E E G F Example6-23 E 3H 0.10 G G G 103 E 0.12 E E G F Example 6-24 G 3H 0.11 G G G 104E 0.12 E E G F Example 6-25 E 3H 0.10 G G G 102 E — — E G F Example 6-26E 3H 0.11 G G G 103 E — — E G F Example 6-27 E 3H 0.09 G G G 102 E — — EE G Example 6-28 E 3H 0.10 G G G 101 E — — E E G Example 6-29 E 3H 0.09G G G 103 E — — E E E Example 6-30 E 3H 0.11 G G G 106 E — — E E EExample 6-31 E 3H 0.09 G G G 104 E — — E G F Example 6-32 E 3H 0.10 G GG 105 E — — E G F Example 6-33 E 3H 0.09 G G G 104 E — — E E G Example6-34 E 3H 0.09 G G G 104 E — — E E E Example 6-35 E 3H 0.09 G G G 105 E— — E E E Comparative F 2H 0.11 P G P 102 E — — E G F Example 3-AComparative F 2H 0.10 P G P 103 E — — E G F Example 3-B Comparative P 3H0.10 G G G 103 E — — E G F Example 3-C Comparative P 3H 0.09 G G G 103 E— — E G F Example 3-D Comparative P 3H 0.12 G G G 102 E 0.06 G E G FExample 3-E Comparative P 2H 0.27 G P P  43 E — — E G F Example 3-FComparative P B 0.29 G G G 106 E — — E G F Example 3-G Comparative P 3H0.10 G G G 103 E — — P P P Example 3-H Comparative P 3H 0.11 G G G 102 E— — P P P Example 3-I Comparative P 3H 0.09 G G G 104 E — — P P PExample 3-J

Example 6-2

Preparation of Coating Solution for Low Refraction Layer

To 93.0 g of a heat crosslinkable fluorine-containing polymer having arefractive index of 1.42 (Opstar JN7228; solid content concentration: 6%by weight, produced by JSR Corporation) were added 8.0 g of a methylethyl ketone dispersion of silica fine particles (MEK-ST, solid contentconcentration: 30% by weight, produced by NISSAN CHEMICAL INDUSTRIES,LTD.), 100.0 g of methyl ethyl ketone and 5.0 g of cyclohexanone. Themixture was then stirred. The mixture was then filtered through a filtermade of polypropylene having a pore diameter of 1 μm to prepare acoating solution for low refraction layer.

Preparation of Anti-Reflection Film

The coating solution for low refraction layer was applied to the highrefraction layer prepared in Example 6-1 using a gravure coater. Thecoated material was dried at 80° C., and then heated to 120° C. for 10minutes to form a low refraction layer (refractive index: 1.43;thickness: 86 nm). Thus, an anti-reflection film was prepared.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-1. The results are shown in Table 3.

Example 6-3

Preparation of Coating Solution for Low Refraction Layer

To 130.0 g of a heat crosslinkable fluorine-containing polymer having arefractive index of 1.42 (Opstar JN7228; solid content concentration: 6%by weight, produced by JSR Corporation) were added 100.0 g of a methylethyl ketone and 5.0 g of cyclohexanone. The mixture was then stirred.The mixture was then filtered through a filter made of polypropylenehaving a pore diameter of 1 μm to prepare a coating solution for lowrefraction layer.

Preparation of Anti-Reflection Film

The coating solution for low refraction layer was applied to the highrefraction layer prepared in Example 6-1 using a gravure coater. Thecoated material was dried at 80° C., and then heated to 120° C. for 10minutes to form a low refraction layer (refractive index: 1.42;thickness: 88 nm). Thus, an anti-reflection film was prepared.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-1. The results are shown in Table 3.

Example 6-4

Preparation of Coating Solution for Stain-Proofing Layer

To 1.0 g of a water-repellent surface active agent (KP801M, produced byShin-Etsu Chemical Co., Ltd.) was added 100.0 g of a fluorine-basedsolvent (Florinate FC-77, produced by Sumitomo 3M). The mixture was thenstirred. The mixture was then filtered through a filter made ofpolypropylene having a pore diameter of 1 μm to prepare a coatingsolution for stain-proofing layer.

Preparation of Anti-Reflection Film

A low refraction layer made of SiO₂ (refractive index: 1.47; thickness:84 nm) was formed on the high refraction layer prepared in Example 6-1by a sputtering method. The coating solution for stain-proofing layerwas applied to the low refraction layer using a bar coater in such anamount that the coated amount of the water-repellent surface treatmentagent reached 15 mg/m². The coated material was then heated to 120° C.for 6 minutes to form a stain-proofing layer. Thus, an anti-reflectionfilm was prepared.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-1. The results are shown in Table 3.

Example 6-5

Preparation of Anti-Reflection Film

The anti-reflection film prepared in Example 6-1 was subjected toembossing according to the method described in examples inJP-A-2000-329905. Thus, an anti-reflection film having an anti-glareperformance was prepared.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-1. Further, the anti-reflection film was evaluated foraverage surface roughness (Ra) and anti-glare performance according tothe following methods. The results are shown in Table 3.

(1) Evaluation of Average Surface Roughness (Ra)

The average surface roughness was evaluated using an atomic forcemicroscope (SPI-3800N AFM; produced by Seiko Instruments Inc.). Theanti-reflection film thus prepared was measured for roughness on theside having a high refraction layer at an area of 100 μm×100 μm randomlysampled from the area of 100 cm². The average surface roughness values(Ra) measured at a total of 100 sites (1 mm² area) were then averaged.

(2) Evaluation of Anti-Glare Performance

An image of an exposed fluorescent lamp free of louver (8,000 cd/cm²)was reflected on the anti-reflection film. The degree of blurriness ofthe reflected image was then evaluated according to the followingcriterion.

-   -   E: The contour of the fluorescent lamp can be little or not        recognized    -   G: The contour of the fluorescent lamp can be slightly        recognized    -   F: The fluorescent lamp is shown blurred, but its contour can be        recognized    -   P: The fluorescent lamp is shown little blurred

Example 6-6

Preparation of Anti-Reflection Film

The anti-reflection film prepared in Example 6-2 was subjected toembossing according to the method described in examples inJP-A-2000-329905. Thus, an anti-reflection film having an anti-glareperformance was prepared.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-5. The results are shown in Table 3.

Example 6-7

Preparation of Coating Solution for High Refraction Layer

To 985.7 g of the dispersion of titanium dioxide prepared in Example 6-1were added 48.8 g of a mixture of dipentaerythritol pentaacrylate anddipentaerythritol hexaacrylate (DPHA, produced by NIPPON KAYAKU CO.,LTD.), 4.03 g of a photopolymerization initiator (Irgacure 907, producedby Cibasophy Ciba-Geigy Japan Limited), 1.35 g of a photosensitizer(Kayacure DETX, produced by NIPPON KAYAKU CO., LTD.), 622.5 g of methylethyl ketone and 1,865.0 g of cyclohexanone. The mixture was thenstirred. The mixture was then filtered through a filter made ofpolypropylene having a pore diameter of 0.4 μm to prepare a coatingsolution for high refraction layer.

Preparation of anti-reflection film

The coating solution for high refraction layer was then applied to themiddle refraction layer prepared in Example 6-1 using a gravure coater.The coated material was dried at 100° C., and then irradiated withultraviolet ray having an illuminance of 550 mW/cm² from a 240 W/cmair-cooled metal halide lamp (produced by EYGRAPHICS CO., LTD.) at adose of 600 mJ/cm² while the air in the reaction vessel was being purgedwith nitrogen to an oxygen concentration of not greater than 1.0% byvolume to cause the coat layer to be cured, thereby forming a highrefraction layer (refractive index: 1.90; thickness: 107 nm).

The coating solution for low refraction layer prepared in Example 6-1was then applied to the high refraction layer using a gravure coater.The coated material was dried at 80° C., irradiated with ultraviolet rayhaving an illuminance of 550 mW/cm² from a 240 W/cm air-cooled metalhalide lamp (produced by EYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm²while the air in the reaction vessel was being purged with nitrogen toan oxygen concentration of not greater than 1.0% by volume, and thenheated to 120° C. for 10 minutes to form a low refraction layer(refractive index: 1.43; thickness: 86 nm). Thus, an anti-reflectionfilm was prepared. In the middle refraction layer and high refractionlayer, the dispersant was crosslinked and/or polymerized with the binderby the aforementioned irradiation with light.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-1. The results are shown in Table 3.

Example 6-8

Preparation of Anti-Reflection Film

The coating solution for low refraction layer prepared in Example 6-2was then applied to the high refraction layer prepared in Example 6-7using a gravure coater. The coated material was dried at 80° C., andthen heated to 120° C. for 10 minutes to form a low refraction layer(refractive index: 1.43; thickness: 86 nm). Thus, an anti-reflectionfilm was prepared.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-1. The results are shown in Table 3.

Example 6-9

Preparation of Dispersion of Titanium Dioxide Fine Particles

To 250 g of titanium dioxide fine particles (TTO-55B, produced byISHIHARA SANGYO KAISHA, LTD.) were added 37.5 g of the dispersant usedin Example 6-1 and 712.5 g of cyclohexanone. The mixture was subjectedto dispersion using a dynomill to prepare a dispersion of titaniumdioxide fine particles having a weight-average diameter of 65 nm.

Preparation of Coating Solution for Middle Refraction Layer

To 155.2 g of the aforementioned dispersion of titanium dioxide wereadded 89.5 g of a mixture of dipentaerythritol pentaacrylate anddipentaerythritol hexaacrylate (DPHA, produced by NIPPON KAYAKU CO.,LTD.), 4.68 g of a photopolymerization initiator (Irgacure 907, producedby Cibasophy Ciba-Geigy Japan Limited), 1.56 g of a photosensitizer(Kayacure DETX, produced by NIPPON KAYAKU CO., LTD.), 770.4 g of methylethyl ketone and 2,983.0 g of cyclohexanone. The mixture was thenstirred. The mixture was then filtered through a filter made ofpolypropylene having a pore diameter of 0.4 μm to prepare a coatingsolution for middle refraction layer.

Preparation of Coating Solution for High Refraction Layer

To 985.7 g of the above dispersion of titanium dioxide were added 48.8 gof a mixture of dipentaerythritol pentaacrylate and dipentaerythritolhexaacrylate (DPHA, produced by NIPPON KAYAKU CO., LTD.), 33.5 g of anacrylic group-containing silane coupling agent (KBM-5103, produced byShin-Etsu Chemical Co., Ltd.), 4.03 g of a photopolymerization initiator(Irgacure 907, produced by Cibasophy Ciba-Geigy Japan Limited), 1.35 gof a photosensitizer (Kayacure DETX, produced by NIPPON KAYAKU CO.,LTD.), 622.5 g of methyl ethyl ketone and 1,865.0 g of cyclohexanone.The mixture was then stirred. The mixture was then filtered through afilter made of polypropylene having a pore diameter of 0.4 μm to preparea coating solution for high refraction layer.

Preparation of Anti-Reflection Film

The coating solution for middle refraction layer was then applied to thehard coat layer prepared in Example 6-1 using a gravure coater. Thecoated material was dried at 100° C., and then irradiated withultraviolet ray having an illuminance of 550 mW/cm² from a 240 W/cmair-cooled metal halide lamp (produced by EYGRAPHICS CO., LTD.) at adose of 600 mJ/cm² while the air in the reaction vessel was being purgedwith nitrogen to an oxygen concentration of not greater than 1.0% byvolume to cause the coat layer to be cured, thereby forming a middlerefraction layer (refractive index: 1.63; thickness: 67 nm).

The coating solution for high refraction layer was then applied to themiddle refraction layer using a gravure coater. The coated material wasdried at 100° C., and then irradiated with ultraviolet ray having anilluminance of 550 mW/cm² from a 240 W/cm air-cooled metal halide lamp(produced by EYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm² while the airin the reaction vessel was being purged with nitrogen to an oxygenconcentration of not greater than 1.0% by volume to cause the coat layerto be cured, thereby forming a high refraction layer (refractive index:1.90; thickness: 107 nm).

The coating solution for low refraction layer prepared in Example 6-1was then applied to the high refraction layer using a gravure coater.The coated material was dried at 80° C., irradiated with ultraviolet rayhaving an illuminance of 550 mW/cm² from a 240 W/cm air-cooled metalhalide lamp (produced by EYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm²while the air in the reaction vessel was being purged with nitrogen toan oxygen concentration of not greater than 1.0% by volume, and thenheated to 120° C. for 10 minutes to form a low refraction layer(refractive index: 1.43; thickness: 86 nm). Thus, an anti-reflectionfilm was prepared. In the middle refraction layer and high refractionlayer, the dispersant was crosslinked and/or polymerized with the binderby the aforementioned irradiation with light.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-1. The results are shown in Table 3.

Example 6-10

Preparation of Anti-Reflection Film

The coating solution for low refraction layer prepared in Example 6-2was applied to the high refraction layer prepared in Example 6-9 using agravure coater. The coated material was dried at 80° C., and then heatedto 120° C. for 10 minutes to form a low refraction layer (refractiveindex: 1.43; thickness: 86 nm). Thus, an anti-reflection film wasprepared.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-1. The results are shown in Table 3.

Example 6-11

Preparation of Anti-Reflection Film

The anti-reflection film prepared in Example 6-9 was subjected toembossing according to the method described in examples inJP-A-2000-329905. Thus, an anti-reflection film having an anti-glareperformance was prepared.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-5. The results are shown in Table 3.

Example 6-12

Preparation of Anti-Reflection Film

The anti-reflection film prepared in Example 6-10 was subjected toembossing according to the method described in examples inJP-A-2000-329905. Thus, an anti-reflection film having an anti-glareperformance was prepared.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-5. The results are shown in Table 3.

Example 6-13

Preparation of Coating Solution for High Refraction Layer

To 985.7 g of the dispersion of titanium dioxide prepared in Example 6-9were added 48.8 g of a mixture of dipentaerythritol pentaacrylate anddipentaerythritol hexaacrylate (DPHA, produced by NIPPON KAYAKU CO.,LTD.), 4.03 g of a photopolymerization initiator (Irgacure 907, producedby Cibasophy Ciba-Geigy Japan Limited), 1.35 g of a photosensitizer(Kayacure DETX, produced by NIPPON KAYAKU CO., LTD.), 622.5 g of methylethyl ketone and 1,865.0 g of cyclohexanone. The mixture was thenstirred. The mixture was then filtered through a filter made ofpolypropylene having a pore diameter of 0.4 μm to prepare a coatingsolution for high refraction layer.

Preparation of Anti-Reflection Film

The coating solution for high refraction layer was then applied to themiddle refraction layer prepared in Example 6-9 using a gravure coater.The coated material was dried at 100° C., and then irradiated withultraviolet ray having an illuminance of 550 mW/cm² from a 240 W/cmair-cooled metal halide lamp (produced by EYGRAPHICS CO., LTD.) at adose of 600 mJ/cm² while the air in the reaction vessel was being purgedwith nitrogen to an oxygen concentration of not greater than 1.0% byvolume to cause the coat layer to be cured, thereby forming a highrefraction layer (refractive index: 1.90; thickness: 107 nm).

The coating solution for low refraction layer prepared in Example 6-1was then applied to the high refraction layer using a gravure coater.The coated material was dried at 80° C., irradiated with ultraviolet rayhaving an illuminance of 550 mW/cm² from a 240 W/cm air-cooled metalhalide lamp (produced by EYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm²while the air in the reaction vessel was being purged with nitrogen toan oxygen concentration of not greater than 1.0% by volume, and thenheated to 120° C. for 10 minutes to form a low refraction layer(refractive index: 1.43; thickness: 86 nm). Thus, an anti-reflectionfilm was prepared. In the middle refraction layer and high refractionlayer, the dispersant was crosslinked and/or polymerized with the binderby the aforementioned irradiation with light.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-1. The results are shown in Table 3.

Example 6-14

Preparation of Anti-Reflection Film

The coating solution for low refraction layer prepared in Example 6-2was applied to the high refraction layer prepared in Example 6-13 usinga gravure coater. The coated material was dried at 80° C., and thenheated to 120° C. for 10 minutes to form a low refraction layer(refractive index: 1.43; thickness: 86 nm). Thus, an anti-reflectionfilm was prepared.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-1. The results are shown in Table 3.

Example 6-15

Preparation of Coating Solution for High Refraction Layer

To 985.7 g of the dispersion of titanium dioxide prepared in Example 6-9were added 48.8 g of a mixture of dipentaerythritol pentaacrylate anddipentaerythritol hexaacrylate (DPHA, produced by NIPPON KAYAKU CO.,LTD.), 5.6 g of an epoxy group-containing silane coupling agent(KBM-5103, produced by Shin-Etsu Chemical Co., Ltd.), 4.03 g of aphotopolymerization initiator (Irgacure 907, produced by CibasophyCiba-Geigy Japan Limited), 1.35 g of a photosensitizer (Kayacure DETX,produced by NIPPON KAYAKU CO., LTD.), 622.5 g of methyl ethyl ketone and1,865.0 g of cyclohexanone. The mixture was then stirred. The mixturewas then filtered through a filter made of polypropylene having a porediameter of 0.4 μm to prepare a coating solution for high refractionlayer.

Preparation of Coating Solution for Low Refraction Layer

To 93.0 g of a heat crosslinkable fluorine-containing polymer having arefractive index of 1.42 (Opstar JN7228; solid content concentration: 6%by weight, produced by JSR Corporation) were added 8.0 g of a methylethyl ketone dispersion of silica fine particles (MEK-ST, solid contentconcentration: 30% by weight, produced by NISSAN CHEMICAL INDUSTRIES,LTD.), 0.8 g of an alkyl group-containing silane coupling agent(KBM-3103C, produced by Shin-Etsu Chemical Co., Ltd.), 100.0 g of methylethyl ketone, and 5.0 g of cyclohexanone. The mixture was then stirred.The mixture was then filtered through a filter made of polypropylenehaving a pore diameter of 1 μm to prepare a coating solution for lowrefraction layer.

Preparation of Anti-Reflection Film

The coating solution for high refraction layer was then applied to themiddle refraction layer prepared in Example 6-9 using a gravure coater.The coated material was dried at 100° C., and then irradiated withultraviolet ray having an illuminance of 550 mW/cm² from a 240 W/cmair-cooled metal halide lamp (produced by EYGRAPHICS CO., LTD.) at adose of 600 mJ/cm² while the air in the reaction vessel was being purgedwith nitrogen to an oxygen concentration of not greater than 1.0% byvolume to cause the coat layer to be cured, thereby forming a highrefraction layer (refractive index: 1.90; thickness: 107 nm).

The coating solution for low refraction layer was then applied to thehigh refraction layer using a gravure coater. The coated material wasdried at 80° C., irradiated with ultraviolet ray having an illuminanceof 550 mW/cm² from a 240 W/cm air-cooled metal halide lamp (produced byEYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm² while the air in thereaction vessel was being purged with nitrogen to an oxygenconcentration of not greater than 1.0% by volume, and then heated to120° C. for 10 minutes to form a low refraction layer (refractive index:1.43; thickness: 86 nm). Thus, an anti-reflection film was prepared. Inthe middle refraction layer and high refraction layer, the dispersantwas crosslinked and/or polymerized with the binder by the aforementionedirradiation with light.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-1. The results are shown in Table 3.

Example 6-16

Preparation of Anti-Reflection Film

The coating solution for low refraction layer prepared in Example 6-2was applied to the high refraction layer prepared in Example 6-15 usinga gravure coater. The coated material was dried at 80° C., and thenheated to 120° C. for 10 minutes to form a low refraction layer(refractive index: 1.43; thickness: 86 nm). Thus, an anti-reflectionfilm was prepared.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-1. The results are shown in Table 3.

Example 6-17

Preparation of Dispersion of Titanium Dioxide Fine Particles

To 250 g of titanium dioxide fine particles (TTO-55B, produced byISHIHARA SANGYO KAISHA, LTD.) were added 37.5 g of the followingdispersant and 712.5 g of cyclohexanone. The mixture was subjected todispersion using a dynomill to prepare a dispersion of titanium dioxidefine particles having a weight-average diameter of 65 nm.

Preparation of Coating Solution for Middle Refraction Layer

To 155.2 g of the above dispersion of titanium dioxide were added 89.5 gof a mixture of dipentaerythritol pentaacrylate and dipentaerythritolhexaacrylate (DPHA, produced by NIPPON KAYAKU CO., LTD.), 4.68 g of aphotopolymerization initiator (Irgacure 907, produced by CibasophyCiba-Geigy Japan Limited), 1.56 g of a photosensitizer (Kayacure DETX,produced by NIPPON KAYAKU CO., LTD.), 770.4 g of methyl ethyl ketone and2,983.0 g of cyclohexanone. The mixture was then stirred. The mixturewas then filtered through a filter made of polypropylene having a porediameter of 0.4 μm to prepare a coating solution for middle refractionlayer.

Preparation of Coating Solution for High Refraction Layer)

To 985.7 g of the aforementioned dispersion of titanium dioxide wereadded 48.8 g of a mixture of dipentaerythritol pentaacrylate anddipentaerythritol hexaacrylate (DPHA, produced by NIPPON KAYAKU CO.,LTD.), 33.5 g of an acrylic group-containing silane coupling agent(KBM-5103, produced by Shin-Etsu Chemical Co., Ltd.), 4.03 g of aphotopolymerization initiator (Irgacure 907, produced by CibasophyCiba-Geigy Japan Limited), 1.35 g of a photosensitizer (Kayacure DETX,produced by NIPPON KAYAKU CO., LTD.), 622.5 g of methyl ethyl ketone and1,865.0 g of cyclohexanone. The mixture was then stirred. The mixturewas then filtered through a filter made of polypropylene having a porediameter of 0.4 μm to prepare a coating solution for high refractionlayer.

Preparation of Anti-Reflection Film

The coating solution for middle refraction layer was then applied to thehard coat layer prepared in Example 6-1 using a gravure coater. Thecoated material was dried at 100° C., and then irradiated withultraviolet ray having an illuminance of 550 mW/cm² from a 240 W/cmair-cooled metal halide lamp (produced by EYGRAPHICS CO., LTD.) at adose of 600 mJ/cm² while the air in the reaction vessel was being purgedwith nitrogen to an oxygen concentration of not greater than 1.0% byvolume to cause the coat layer to be cured, thereby forming a middlerefraction layer (refractive index: 1.63; thickness: 67 nm).

The coating solution for high refraction layer was then applied to themiddle refraction layer using a gravure coater. The coated material wasdried at 100° C., and then irradiated with ultraviolet ray having anilluminance of 550 mW/cm² from a 240 W/cm air-cooled metal halide lamp(produced by EYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm² while the airin the reaction vessel was being purged with nitrogen to an oxygenconcentration of not greater than 1.0% by volume to cause the coat layerto be cured, thereby forming a high refraction layer (refractive index:1.90; thickness: 107 nm).

The coating solution for low refraction layer prepared in Example 6-1was then applied to the high refraction layer using a gravure coater.The coated material was dried at 80° C., irradiated with ultraviolet rayhaving an illuminance of 550 mW/cm² from a 240 W/cm air-cooled metalhalide lamp (produced by EYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm²while the air in the reaction vessel was being purged with nitrogen toan oxygen concentration of not greater than 1.0% by volume, and thenheated to 120° C. for 10 minutes to form a low refraction layer(refractive index: 1.43; thickness: 86 nm). Thus, an anti-reflectionfilm was prepared. In the middle refraction layer and high refractionlayer, the dispersant was crosslinked and/or polymerized with the binderby the aforementioned irradiation with light.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-1. The results are shown in Table 3.

Example 6-18

Preparation of Dispersion of Titanium Dioxide Fine Particles

To 250 g of titanium dioxide fine particles (TTO-55B, produced byISHIHARA SANGYO KAISHA, LTD.) were added 37.5 g of the followingdispersant and 712.5 g of cyclohexanone. The mixture was subjected todispersion using a dynomill to prepare a dispersion of titanium dioxidefine particles having a weight-average diameter of 65 nm.

Preparation of Coating Solution for Middle Refraction Layer

To 155.2 g of the above dispersion of titanium dioxide were added 89.5 gof a mixture of dipentaerythritol pentaacrylate and dipentaerythritolhexaacrylate (DPHA, produced by NIPPON KAYAKU CO., LTD.), 4.68 g of aphotopolymerization initiator (Irgacure 907, produced by CibasophyCiba-Geigy Japan Limited), 1.56 g of a photosensitizer (Kayacure DETX,produced by NIPPON KAYAKU CO., LTD.), 770.4 g of methyl ethyl ketone and2,983.0 g of cyclohexanone. The mixture was then stirred. The mixturewas then filtered through a filter made of polypropylene having a porediameter of 0.4 μm to prepare a coating solution for middle refractionlayer.

Preparation of Coating Solution for High Refraction Layer

To 985.7 g of the above dispersion of titanium dioxide were added 48.8 gof a mixture of dipentaerythritol pentaacrylate and dipentaerythritolhexaacrylate (DPHA, produced by NIPPON KAYAKU CO., LTD.), 4.03 g of aphotopolymerization initiator (Irgacure 907, produced by CibasophyCiba-Geigy Japan Limited), 1.35 g of a photosensitizer (Kayacure DETX,produced by NIPPON KAYAKU CO., LTD.), 622.5 g of methyl ethyl ketone and1,865.0 g of cyclohexanone. The mixture was then stirred. The mixturewas then filtered through a filter made of polypropylene having a porediameter of 0.4 μm to prepare a coating solution for high refractionlayer.

Preparation of Anti-Reflection Film

The coating solution for middle refraction layer was then applied to thehard coat layer prepared in Example 6-1 using a gravure coater. Thecoated material was dried at 100° C., and then irradiated withultraviolet ray having an illuminance of 550 mW/cm² from a 240 W/cmair-cooled metal halide lamp (produced by EYGRAPHICS CO., LTD.) at adose of 600 mJ/cm² while the air in the reaction vessel was being purgedwith nitrogen to an oxygen concentration of not greater than 1.0% byvolume to cause the coat layer to be cured, thereby forming a middlerefraction layer (refractive index: 1.63; thickness: 67 nm).

The coating solution for high refraction layer was then applied to themiddle refraction layer using a gravure coater. The coated material wasdried at 100° C., and then irradiated with ultraviolet ray having anilluminance of 550 mW/cm² from a 240 W/cm air-cooled metal halide lamp(produced by EYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm² while the airin the reaction vessel was being purged with nitrogen to an oxygenconcentration of not greater than 1.0% by volume to cause the coat layerto be cured, thereby forming a high refraction layer (refractive index:1.90; thickness: 107 nm).

The coating solution for low refraction layer prepared in Example 6-1was then applied to the high refraction layer using a gravure coater.The coated material was dried at 80° C., irradiated with ultraviolet rayhaving an illuminance of 550 mW/cm² from a 240 W/cm air-cooled metalhalide lamp (produced by EYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm²while the air in the reaction vessel was being purged with nitrogen toan oxygen concentration of not greater than 1.0% by volume, and thenheated to 120° C. for 10 minutes to form a low refraction layer(refractive index: 1.43; thickness: 86 nm). Thus, an anti-reflectionfilm was prepared. In the middle refraction layer and high refractionlayer, the dispersant was crosslinked and/or polymerized with the binderby the aforementioned irradiation with light.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-1. The results are shown in Table 3.

Example 6-19

Preparation of Dispersion of Titanium Dioxide Fine Particles

To 250 g of titanium dioxide fine particles (TTO-55B, produced byISHIHARA SANGYO KAISHA, LTD.) were added 37.5 g of the followingdispersant and 712.5 g of cyclohexanone. The mixture was subjected todispersion using a dynomill to prepare a dispersion of titanium dioxidefine particles having a weight-average diameter of 65 nm.

Preparation of Coating Solution for Middle Refraction Layer

To 155.2 g of the above dispersion of titanium dioxide were added 89.5 gof a mixture of dipentaerythritol pentaacrylate and dipentaerythritolhexaacrylate (DPHA, produced by NIPPON KAYAKU CO., LTD.), 4.68 g of aphotopolymerization initiator (Irgacure 907, produced by CibasophyCiba-Geigy Japan Limited), 1.56 g of a photosensitizer (Kayacure DETX,produced by NIPPON KAYAKU CO., LTD.), 770.4 g of methyl ethyl ketone and2,983.0 g of cyclohexanone. The mixture was then stirred. The mixturewas then filtered through a filter made of polypropylene having a porediameter of 0.4 μm to prepare a coating solution for middle refractionlayer.

Preparation of Coating Solution for High Refraction Layer

To 985.7 g of the above dispersion of titanium dioxide were added 48.8 gof a mixture of dipentaerythritol pentaacrylate and dipentaerythritolhexaacrylate (DPHA, produced by NIPPON KAYAKU CO., LTD.), 4.03 g of aphotopolymerization initiator (Irgacure 907, produced by CibasophyCiba-Geigy Japan Limited), 1.35 g of a photosensitizer (Kayacure DETX,produced by NIPPON KAYAKU CO., LTD.), 622.5 g of methyl ethyl ketone and1,865.0 g of cyclohexanone. The mixture was then stirred. The mixturewas then filtered through a filter made of polypropylene having a porediameter of 0.4 μm to prepare a coating solution for high refractionlayer.

Preparation of Anti-Reflection Film

The coating solution for middle refraction layer was then applied to thehard coat layer prepared in Example 6-1 using a gravure coater. Thecoated material was dried at 100° C., and then irradiated withultraviolet ray having an illuminance of 550 mW/cm² from a 240 W/cmair-cooled metal halide lamp (produced by EYGRAPHICS CO., LTD.) at adose of 600 mJ/cm² while the air in the reaction vessel was being purgedwith nitrogen to an oxygen concentration of not greater than 1.0% byvolume to cause the coat layer to be cured, thereby forming a middlerefraction layer (refractive index: 1.63; thickness: 67 nm).

The coating solution for high refraction layer was then applied to themiddle refraction layer using a gravure coater. The coated material wasdried at 100° C., and then irradiated with ultraviolet ray having anilluminance of 550 mW/cm² from a 240 W/cm air-cooled metal halide lamp(produced by EYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm² while the airin the reaction vessel was being purged with nitrogen to an oxygenconcentration of not greater than 1.0% by volume to cause the coat layerto be cured, thereby forming a high refraction layer (refractive index:1.90; thickness: 107 nm).

The coating solution for low refraction layer prepared in Example 6-1was then applied to the high refraction layer using a gravure coater.The coated material was dried at 80° C., irradiated with ultraviolet rayhaving an illuminance of 550 mW/cm² from a 240 W/cm air-cooled metalhalide lamp (produced by EYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm²while the air in the reaction vessel was being purged with nitrogen toan oxygen concentration of not greater than 1.0% by volume, and thenheated to 120° C. for 10 minutes to form a low refraction layer(refractive index: 1.43; thickness: 86 nm). Thus, an anti-reflectionfilm was prepared. In the middle refraction layer and high refractionlayer, the dispersant was crosslinked and/or polymerized with the binderby the aforementioned irradiation with light.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-1. The results are shown in Table 3.

Example 6-20

Preparation of Dispersion of Titanium Dioxide Fine Particles

To 250 g of titanium dioxide fine particles (TTO-55B, produced byISHIHARA SANGYO KAISHA, LTD.) were added 37.5 g of the followingdispersant and 712.5 g of cyclohexanone. The mixture was subjected todispersion using a dynomill to prepare a dispersion of titanium dioxidefine particles having a weight-average diameter of 65 nm.

Preparation of Coating Solution for Middle Refraction Layer

To 155.2 g of the above dispersion of titanium dioxide were added 89.5 gof a mixture of dipentaerythritol pentaacrylate and dipentaerythritolhexaacrylate (DPHA, produced by NIPPON KAYAKU CO., LTD.), 4.68 g of aphotopolymerization initiator (Irgacure 907, produced by CibasophyCiba-Geigy Japan Limited), 1.56 g of a photosensitizer (Kayacure DETX,produced by NIPPON KAYAKU CO., LTD.), 770.4 g of methyl ethyl ketone and2,983.0 g of cyclohexanone. The mixture was then stirred. The mixturewas then filtered through a filter made of polypropylene having a porediameter of 0.4 μm to prepare a coating solution for middle refractionlayer.

Preparation of Coating Solution for High Refraction Layer

To 985.7 g of the above dispersion of titanium dioxide were added 48.8 gof a mixture of dipentaerythritolpentaacrylate and dipentaerythritolhexaacrylate (DPHA, produced by NIPPON KAYAKU CO., LTD.), 4.03 g of aphotopolymerization initiator (Irgacure 907, produced by CibasophyCiba-Geigy Japan Limited), 1.35 g of a photosensitizer (Kayacure DETX,produced by NIPPON KAYAKU CO., LTD.), 622.5 g of methyl ethyl ketone and1,865.0 g of cyclohexanone. The mixture was then stirred. The mixturewas then filtered through a filter made of polypropylene having a porediameter of 0.4 μm to prepare a coating solution for high refractionlayer.

Preparation of Anti-Reflection Film

The coating solution for middle refraction layer was then applied to thehard coat layer prepared in Example 6-1 using a gravure coater. Thecoated material was dried at 100° C., and then irradiated withultraviolet ray having an illuminance of 550 mW/cm² from a 240 W/cmair-cooled metal halide lamp (produced by EYGRAPHICS CO., LTD.) at adose of 600 mJ/cm² while the air in the reaction vessel was being purgedwith nitrogen to an oxygen concentration of not greater than 1.0% byvolume to cause the coat layer to be cured, thereby forming a middlerefraction layer (refractive index: 1.63; thickness: 67 nm).

The coating solution for high refraction layer was then applied to themiddle refraction layer using a gravure coater. The coated material wasdried at 100° C., and then irradiated with ultraviolet ray having anilluminance of 550 mW/cm² from a 240 W/cm air-cooled metal halide lamp(produced by EYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm² while the airin the reaction vessel was being purged with nitrogen to an oxygenconcentration of not greater than 1.0% by volume to cause the coat layerto be cured, thereby forming a high refraction layer (refractive index:1.90; thickness: 107 nm).

The coating solution for low refraction layer prepared in Example 6-1was then applied to the high refraction layer using a gravure coater.The coated material was dried at 80° C., irradiated with ultraviolet rayhaving an illuminance of 550 mW/cm² from a 240 W/cm air-cooled metalhalide lamp (produced by EYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm²while the air in the reaction vessel was being purged with nitrogen toan oxygen concentration of not greater than 1.0% by volume, and thenheated to 120° C. for 10 minutes to form a low refraction layer(refractive index: 1.43; thickness: 86 nm). Thus, an anti-reflectionfilm was prepared. In the middle refraction layer and high refractionlayer, the dispersant was crosslinked and/or polymerized with the binderby the aforementioned irradiation with light.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-1. The results are shown in Table 3.

Example 6-21

Preparation of Coating Solution for Hard Coat Layer

To 625.0 g of a hard coat layer material (DeSolite Z7526; solid contentconcentration: 72% by weight, produced by JSR Corporation) were added155.0 g of methyl ethyl ketone and 220.0 g of cyclohexanone. The mixturewas then stirred. The mixture was then filtered through a filter made ofpolypropylene having a pore diameter of 0.4 μm to prepare a coatingsolution for hard coat layer.

Preparation of Dispersion of Zirconium Oxide

To 200.0 g of a zirconium oxide powder having a weight-average primaryparticle diameter of 30 nm were added 60.0 g of a dispersant (ka-14) and740 g of cyclohexanone. The mixture was then subjected to dispersionusing a dynomill to prepare a dispersion of zirconium oxide having aweight-average particle diameter of 40 nm.

Preparation of Coating Solution for Anti-Glare Layer

20.0 g of crosslinked polystyrene particles having an average particlediameter of 2 μm (SX-200H, produced by Soken Chemical & Engineering Co.,Ltd.) was added to a 54/46 (by weight) mixture of methyl ethyl ketoneand cyclohexanone. The mixture was then stirred at 5,000 rpm using ahigh speed disper to prepare a dispersion of crosslinked polystyrenefine particles.

To 355.8 g of the above dispersion of zirconium oxide were added 104.0 gof a mixture of dipentaerythritol pentaacrylate and dipentaerythritolhexaacrylate (DPHA, produced by NIPPON KAYAKU CO., LTD.) and 12.0 g of aphotopolymerization initiator (Irgacure 907, produced by CibasophyCiba-Geigy Japan Limited). The mixture was then stirred. The coat layerobtained by the application and ultraviolet curing of this solution hada refractive index of 1.61.

To this solution was then added 29.0 g of the dispersion of crosslinkedpolystyrene particles prepared above. The mixture was then stirred. Themixture was then filtered through a filter made of polypropylene havinga pore diameter of 30 μm to prepare a coating solution for anti-glarelayer.

Preparation of Anti-Reflection Film

The coating solution for hard coat layer was applied to a triacetylcellulose film having a thickness of 80 μm (TD-80UF, produced by FujiPhoto Film Co., Ltd.) using a gravure coater. The coated material wasdried at 100° C., and then irradiated with ultraviolet ray having anilluminance of 400 mW/cm² from a 160 W/cm air-cooled metal halide lamp(produced by EYGRAPHICS CO., LTD.) at a dose of 300 mJ/cm² to cause thecoat layer to be cured, thereby forming a hard coat layer having athickness of 3.5 μm.

The coating solution for anti-glare layer was applied to the hard coatlayer using a gravure coater. The coated material was dried at 90° C.,and then irradiated with ultraviolet ray having an illuminance of 550mW/cm² from a 240 W/cm air-cooled metal halide lamp (produced byEYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm² while the air in thereaction vessel was being purged with nitrogen to an oxygenconcentration of not greater than 2% by volume to cause the coat layerto be cured, thereby forming an anti-glare layer having a haze of 17%.

The coating solution for low refraction layer prepared in Example 6-1was then applied to the anti-glare layer using a gravure coater. Thecoated material was dried at 80° C., irradiated with ultraviolet rayhaving an illuminance of 550 mW/cm² from a 240 W/cm air-cooled metalhalide lamp (produced by EYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm²while the air in the reaction vessel was being purged with nitrogen toan oxygen concentration of not greater than 1.0% by volume, and thenheated to 120° C. for 10 minutes to form a low refraction layer having athickness of 96 nm. Thus, an anti-reflection film was prepared. In theanti-glare layer, the dispersant was crosslinked and/or polymerized withthe binder by the aforementioned irradiation with light.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-5. The results are shown in Table 3.

Example 6-22

Preparation of Anti-Reflection Film

The coating solution for low refraction film prepared in Example 6-2 wasapplied to the anti-glare layer prepared in Example 6-21 using a gravurecoater. The coated material was dried at 80° C., and then further heatedto 120° C. for 10 minutes to form a low refraction layer having athickness of 96 nm. Thus, an anti-reflection film was prepared.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was then evaluated in the samemanner as in Example 6-5. The results are shown in Table 3.

Example 6-23

Preparation of Dispersion of ATO

To 200.0 g of ATO fine particles (SN-100P, produced by ISHIHARA SANGYOKAISHA, LTD.) were added 40.0 g of the following dispersant, 2.7 g of acationic monomer (DMAEA, produced by KOHJIN Co., Ltd.) and 760 g ofcyclohexanone. The mixture was then subjected to dispersion using adynomill to prepare a dispersion of ATO having a weight-average diameterof 40 nm.

Preparation of Coating Solution for Anti-Glare Layer

200.0 g of crosslinked polystyrene particles having an average particlediameter of 3.5 μm (SX-350H, produced by Soken Chemical & EngineeringCo., Ltd.) was added to 800.0 g of methyl isobutyl ketone. The mixturewas then stirred at 10,000 rpm for 1 hour using a polytron dispersingmachine to prepare a dispersion A of crosslinked polystyrene particles.

200.0 g of crosslinked polystyrene particles having an average particlediameter of 5.0 μm (SX-500H, produced by Soken Chemical & EngineeringCo., Ltd.) was added to 800.0 g of methyl isobutyl ketone. The mixturewas then stirred at 10,000 rpm for 1 hour using a polytron dispersingmachine to prepare a dispersion B of crosslinked polystyrene particles.

To 335.0 g of the above dispersion of ATO were added 96.0 g of a mixtureof dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate(DPHA, produced by NIPPON KAYAKU CO., LTD.), 11.0 g of aphotopolymerization initiator (Irgacure 184, produced by CibasophyCiba-Geigy Japan Limited) and 19.6 g of an acrylic group-containingsilane coupling agent (KBM-5103, produced by Shin-Etsu Chemical Co.,Ltd.). The coat layer obtained by the application and ultraviolet curingof this solution had a refractive index of 1.57.

To this solution were then added 55.0 g of the dispersion A ofcrosslinked polystyrene particles prepared above and 72.3 g of thedispersion B of crosslinked polystyrene particles prepared above. Themixture was then stirred. The mixture was then filtered through a filtermade of polypropylene having a pore diameter of 30 μm to prepare acoating solution for anti-glare layer.

Preparation of Anti-Reflection Film

The coating solution for anti-glare layer was applied to a triacetylcellulose film having a thickness of 80 μm (TD-80UF, produced by FujiPhoto Film Co., Ltd.) using a gravure coater. The coated material wasdried at 90° C., and then irradiated with ultraviolet ray having anilluminance of 550 mW/cm² from a 240 W/cm air-cooled metal halide lamp(produced by EYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm² while the airin the reaction vessel was being purged with nitrogen to an oxygenconcentration of not greater than 1.0% by volume to cause the coat layerto be cured, thereby forming an anti-glare layer having a haze of 44.5%.

The coating solution for low refraction layer prepared in Example 6-1was then applied to the anti-glare layer using a gravure coater. Thecoated material was dried at 80° C., irradiated with ultraviolet rayhaving an illuminance of 550 mW/cm² from a 240 W/cm air-cooled metalhalide lamp (produced by EYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm²while the air in the reaction vessel was being purged with nitrogen toan oxygen concentration of not greater than 1.0% by volume, and thenheated to 120° C. for 10 minutes to form a low refraction layer having athickness of 96 nm. Thus, an anti-reflection film was prepared. In theanti-glare layer, the dispersant was crosslinked and/or polymerized withthe binder by the aforementioned irradiation with light.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-5. The results are shown in Table 3.

Example 6-24

Preparation of Anti-Reflection Film

The coating solution for low refraction film prepared in Example 6-2 wasapplied to the anti-glare layer prepared in Example 6-23 using a gravurecoater. The coated material was dried at 80° C., and then further heatedto 120° C. for 10 minutes to form a low refraction layer having athickness of 96 nm. Thus, an anti-reflection film was prepared.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was then evaluated in the samemanner as in Example 6-5. The results are shown in Table 3.

Example 6-25

Preparation of Dispersion of Titanium Dioxide Fine Particles

To 257.1 g of titanium dioxide fine particles (MT-500HD, produced byTAYCA CORPORATION) were then added 38.6 g of the dispersant used inExample 6-1 and 704.3 g of cyclohexanone. The mixture was then subjectedto dispersion using a dynomill to prepare a dispersion of titaniumdioxide having a weight-average diameter of 75 nm.

Preparation of Coating Solution for Middle Refraction Layer

To 151.1 g of the above dispersion of titanium dioxide were added 89.5 gof a mixture of dipentaerythritol pentaacrylate and dipentaerythritolhexaacrylate (DPHA, produced by NIPPON KAYAKU CO., LTD.), 4.68 g of aphotopolymerization initiator (Irgacure 907, produced by CibasophyCiba-Geigy Japan Limited), 1.56 g of a photosensitizer (Kayacure DETX,produced by NIPPON KAYAKU CO., LTD.), 770.4 g of methyl ethyl ketone and2,983.0 g of cyclohexanone. The mixture was then stirred. The mixturewas then filtered through a filter made of polypropylene having a porediameter of 0.4 μm to prepare a coating solution for middle refractionlayer.

Preparation of Coating Solution for High Refraction Layer

To 959.2 g of the above dispersion of titanium dioxide were added 48.8 gof a mixture of dipentaerythritol pentaacrylate and dipentaerythritolhexaacrylate (DPHA, produced by NIPPON KAYAKU CO., LTD.), 4.03 g of aphotopolymerization initiator (Irgacure 907, produced by CibasophyCiba-Geigy Japan Limited), 1.35 g of a photosensitizer (Kayacure DETX,produced by NIPPON KAYAKU CO., LTD.), 622.5 g of methyl ethyl ketone and1,865.0 g of cyclohexanone. The mixture was then stirred. The mixturewas then filtered through a filter made of polypropylene having a porediameter of 0.4 μm to prepare a coating solution for high refractionlayer.

Preparation of Silane Compound

In a reaction vessel equipped with an agitator and a reflux condenserwere charged and mixed 161 parts by weight of3-acryloxypropyltrimethoxysilane (KBM-5103, produced by Shin-EtsuChemical Co., Ltd.), 123 parts by weight of oxalic acid and 415 parts byweight of ethanol. The mixture was reacted at 70° C. for 4 hours, andthen cooled to room temperature to obtain a transparent silane compoundas a curable composition. The silane compound thus obtained had aweight-average molecular weight of 1,600, and the components having amolecular weight of from 1,000 to 20,000 account for 100% of theoligomer or higher components. The gas chromatography of the silanecompound showed that 3-acryloxypropyltrimethoxysilane as a startingmaterial had not been left therein.

Preparation of Coating Solution for Low Refraction Film

A heat crosslinkable fluorine-containing polymer having a refractiveindex of 1.42 (Opstar JN7228; solid content concentration: 6% by weight,produced by JSR Corporation) was subjected to solvent substitution toobtain a methyl isobutyl ketone solution of heat crosslinkable fluorinepolymer having a solid content concentration of 10% by weight. To 56.0 gof the aforementioned heat crosslinkable fluorine polymer solution werethen added 8.0 g of a methyl ethyl ketone dispersion of silica fineparticles (MEK-ST, solid content concentration: 30% by weight, producedby NISSAN CHEMICAL INDUSTRIES, LTD.), 1.75 g of the above silanecompound, 73.0 g of methyl isobutyl ketone and 33.0 g of cyclohexanone.The mixture was then stirred. The mixture was then filtered through afilter made of polypropylene having a pore diameter of 1 μm to prepare acoating solution for low refraction layer.

Preparation of Anti-Reflection Film

The coating solution for middle refraction layer was applied to the hardcoat layer prepared in Example 6-1 using a gravure coater. The coatedmaterial was dried at 100° C., and then irradiated with ultraviolet rayhaving an illuminance of 550 mW/cm² from a 240 W/cm air-cooled metalhalide lamp (produced by EYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm²while the air in the reaction vessel was being purged with nitrogen toan oxygen concentration of not greater than 1.0% by volume to cause thecoat layer to be cured, thereby forming a middle refraction layer(refractive index: 1.63; thickness: 67 nm).

The coating solution for high refraction layer was then applied to themiddle refraction layer using a gravure coater. The coated material wasdried at 100° C., and then irradiated with ultraviolet ray having anilluminance of 550 mW/cm² from a 240 W/cm air-cooled metal halide lamp(produced by EYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm² while the airin the reaction vessel was being purged with nitrogen to an oxygenconcentration of not greater than 1.0% by volume to cause the coat layerto be cured, thereby forming a high refraction layer (refractive index:1.90; thickness: 107 nm).

The coating solution for low refraction layer was then applied to thehigh refraction layer using a gravure coater. The coated material wasdried at 80° C., irradiated with ultraviolet ray having an illuminanceof 550 mW/cm² from a 240 W/cm air-cooled metal halide lamp (produced byEYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm² while the air in thereaction vessel was being purged with nitrogen to an oxygenconcentration of not greater than 1.0% by volume, and then heated to120° C. for 10 minutes to form a low refraction layer (refractive index:1.43; thickness: 86 nm)). Thus, an anti-reflection film was prepared. Inthe middle refraction layer and high refraction layer, the dispersantwas crosslinked and/or polymerized with the binder by the aforementionedirradiation with light.

Evaluation of Anti-Reflection Film

The anti-reflection films thus prepared were then evaluated in the samemanner as in Example 6-1. The results are shown in Table 3.

Example 6-26

Preparation of Coating Solution for Low Refraction Film

A heat crosslinkable fluorine-containing polymer having a refractiveindex of 1.42 (Opstar JN7228; solid content concentration: 6% by weight,produced by JSR Corporation) was subjected to solvent substitution toobtain a methyl isobutyl ketone solution of heat crosslinkable fluorinepolymer having a solid content concentration of 10% by weight. To 56.0 gof the above heat crosslinkable fluorine polymer solution were thenadded 8.0 g of a methyl ethyl ketone dispersion of silica fine particles(MEK-ST, solid content concentration: 30% by weight, produced by NISSANCHEMICAL INDUSTRIES, LTD.), 73.0 g of methyl isobutyl ketone and 33.0 gof cyclohexanone. The mixture was then stirred. The mixture was thenfiltered through a filter made of polypropylene having a pore diameterof 1 μm to prepare a coating solution for low refraction layer.

Preparation of Anti-Reflection Film

The coating solution for low refraction film thus prepared was appliedto the high refraction layer prepared in Example 6-25 using a gravurecoater. The coated material was dried at 80° C., and then heated to 120°C. for 10 minutes to form a low refraction layer (refractive index:1.43; thickness: 86 nm). Thus, an anti-reflection film was prepared.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was then evaluated in the samemanner as in Example 6-1. The results are shown in Table 3.

Example 6-27

Preparation of Titanium Dioxide Fine Particles

Cobalt-containing titanium dioxide fine particles doped with cobalttherein were prepared according to a known method for the preparation oftitanium dioxide fine particles and a known doping method(JP-A-5-330825) except that iron (Fe) was replaced by cobalt.

The doped amount of cobalt was 100/2 as calculated in terms of Ti/Co (byweight).

The titanium dioxide fine particles thus prepared were recognized tohave a rutile type crystal structure and had an average primary particlesize of 41 nm and a specific surface area of 45 m²/g.

Preparation of Dispersion of Titanium Dioxide Fine Particles

To 257.1 g of the above particles were then added 38.6 g of thedispersant used in Example 6-1 and 704.3 g of cyclohexanone. The mixturewas then subjected to dispersion using a dynomill to prepare adispersion of titanium dioxide having a weight-average diameter of 70nm.

Preparation of Coating Solution for Middle Refraction Layer

To 151.1 g of the above dispersion of titanium dioxide were added 89.5 gof a mixture of dipentaerythritol pentaacrylate and dipentaerythritolhexaacrylate (DPHA, produced by NIPPON KAYAKU CO., LTD.), 4.68 g of aphotopolymerization initiator (Irgacure 907, produced by CibasophyCiba-Geigy Japan Limited), 1.56 g of a photosensitizer (Kayacure DETX,produced by NIPPON KAYAKU CO., LTD.), 770.4 g of methyl ethyl ketone and2,983.0 g of cyclohexanone. The mixture was then stirred. The mixturewas then filtered through a filter made of polypropylene having a porediameter of 0.4 μm to prepare a coating solution for middle refractionlayer.

Preparation of Coating Solution for High Refraction Layer

To 959.2 g of the above dispersion of titanium dioxide were added 48.8 gof a mixture of dipentaerythritol pentaacrylate and dipentaerythritolhexaacrylate (DPHA, produced by NIPPON KAYAKU CO., LTD.), 4.03 g of aphotopolymerization initiator (Irgacure 907, produced by CibasophyCiba-Geigy Japan Limited), 1.35 g of a photosensitizer (Kayacure DETX,produced by NIPPON KAYAKU CO., LTD.), 622.5 g of methyl ethyl ketone and1,865.0 g of cyclohexanone. The mixture was then stirred. The mixturewas then filtered through a filter made of polypropylene having a porediameter of 0.4 μm to prepare a coating solution for high refractionlayer.

Preparation of Anti-Reflection Film

The coating solution for middle refraction layer was applied to the hardcoat layer prepared in Example 6-1 using a gravure coater. The coatedmaterial was dried at 100° C., and then irradiated with ultraviolet rayhaving an illuminance of 550 mW/cm² from a 240 W/cm air-cooled metalhalide lamp (produced by EYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm²while the air in the reaction vessel was being purged with nitrogen toan oxygen concentration of not greater than 1.0% by volume to cause thecoat layer to be cured, thereby forming a middle refraction layer(refractive index: 1.63; thickness: 67 nm).

The coating solution for high refraction layer was then applied to themiddle refraction layer using a gravure coater. The coated material wasdried at 100° C., and then irradiated with ultraviolet ray having anilluminance of 550 mW/cm² from a 240 W/cm air-cooled metal halide lamp(produced by EYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm² while the airin the reaction vessel was being purged with nitrogen to an oxygenconcentration of not greater than 1.0% by volume to cause the coat layerto be cured, thereby forming a high refraction layer (refractive index:1.91; thickness: 107 nm).

The coating solution for low refraction layer prepared in Example 6-25was then applied to the high refraction layer using a gravure coater.The coated material was dried at 80° C., irradiated with ultraviolet rayhaving an illuminance of 550 mW/cm² from a 240 W/cm air-cooled metalhalide lamp (produced by EYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm²while the air in the reaction vessel was being purged with nitrogen toan oxygen concentration of not greater than 1.0% by volume, and thenheated to 120° C. for 10 minutes to form a low refraction layer(refractive index: 1.43; thickness: 86 nm). Thus, an anti-reflectionfilm was prepared. In the middle refraction layer and high refractionlayer, the dispersant was crosslinked and/or polymerized with the binderby the aforementioned irradiation with light.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-1. The results are shown in Table 3.

Example 6-28

Preparation of Anti-Reflection Film

The coating solution for low refraction layer prepared in Example 6-26was applied to the high refraction layer prepared in Example 6-27 usinga gravure coater. The coated material was dried at 80° C., and thenheated to 120° C. for 10 minutes to form a low refraction layer(refractive index: 1.43; thickness: 86 nm). Thus, an anti-reflectionfilm was prepared.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-1. The results are shown in Table 3.

Example 6-29

Preparation of Titanium Dioxide Fine Particles

Cobalt-containing titanium dioxide fine particles doped with cobalttherein were prepared according to a known method for the preparation oftitanium dioxide fine particles and a known doping method(JP-A-5-330825) except that iron (Fe) was replaced by cobalt.

The doped amount of cobalt was 100/2 as calculated in terms of Ti/Co (byweight).

The titanium dioxide fine particles thus prepared were recognized tohave a rutile type crystal structure and had an average primary particlesize of 41 nm and a specific surface area of 45 m²/g.

The particles thus prepared were then subjected to surface treatmentwith a surface treatment agent (aluminum hydroxide/zirconiumhydroxide=6/1.5 (by weight)) in such a manner that the ratio of titaniumdioxide/surface treatment reached 100/3.5 (by weight).

Preparation of Dispersion of Titanium Dioxide Fine Particles

The particles thus prepared were then subjected to dispersion in thesame manner as in Example 6-27 to prepare a dispersion of titaniumdioxide having a weight-average diameter of 70 nm.

Preparation of Coating Solution for Middle Refraction Layer

To 151.1 g of the above dispersion of titanium dioxide were added 89.5 gof a mixture of dipentaerythritol pentaacrylate and dipentaerythritolhexaacrylate (DPHA, produced by NIPPON KAYAKU CO., LTD.), 4.68 g of aphotopolymerization initiator (Irgacure 907, produced by CibasophyCiba-Geigy Japan Limited), 1.56 g of a photosensitizer (Kayacure DETX,produced by NIPPON KAYAKU CO., LTD.), 770.4 g of methyl ethyl ketone and2,983.0 g of cyclohexanone. The mixture was then stirred. The mixturewas then filtered through a filter made of polypropylene having a porediameter of 0.4 μm to prepare a coating solution for middle refractionlayer.

Preparation of Coating Solution for High Refraction Layer

To 959.2 g of the above dispersion of titanium dioxide were added 48.8 gof a mixture of dipentaerythritol pentaacrylate and dipentaerythritolhexaacrylate (DPHA, produced by NIPPON KAYAKU CO., LTD.), 4.03 g of aphotopolymerization initiator (Irgacure 907, produced by CibasophyCiba-Geigy Japan Limited), 1.35 g of a photosensitizer (Kayacure DETX,produced by NIPPON KAYAKU CO., LTD.), 622.5 g of methyl ethyl ketone and1,865.0 g of cyclohexanone. The mixture was then stirred. The mixturewas then filtered through a filter made of polypropylene having a porediameter of 0.4 μm to prepare a coating solution for high refractionlayer.

Preparation of Anti-Reflection Film

The coating solution for middle refraction layer was applied to the hardcoat layer prepared in Example 6-1 using a gravure coater. The coatedmaterial was dried at 100° C., and then irradiated with ultraviolet rayhaving an illuminance of 550 mW/cm² from a 240 W/cm air-cooled metalhalide lamp (produced by EYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm²while the air in the reaction vessel was being purged with nitrogen toan oxygen concentration of not greater than 1.0% by volume to cause thecoat layer to be cured, thereby forming a middle refraction layer(refractive index: 1.64; thickness: 67 nm).

The coating solution for high refraction layer was then applied to themiddle refraction layer using a gravure coater. The coated material wasdried at 100° C., and then irradiated with ultraviolet ray having anilluminance of 550 mW/cm² from a 240 W/cm air-cooled metal halide lamp(produced by EYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm² while the airin the reaction vessel was being purged with nitrogen to an oxygenconcentration of not greater than 1.0% by volume to cause the coat layerto be cured, thereby forming a high refraction layer (refractive index:1.90; thickness: 107 nm).

The coating solution for low refraction layer prepared in Example 6-25was then applied to the high refraction layer using a gravure coater.The coated material was dried at 80° C., irradiated with ultraviolet rayhaving an illuminance of 550 mW/cm² from a 240 W/cm air-cooled metalhalide lamp (produced by EYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm²while the air in the reaction vessel was being purged with nitrogen toan oxygen concentration of not greater than 1.0% by volume, and thenheated to 120° C. for 10 minutes to form a low refraction layer(refractive index: 1.43; thickness: 86 nm). Thus, an anti-reflectionfilm was prepared. In the middle refraction layer and high refractionlayer, the dispersant was crosslinked and/or polymerized with the binderby the aforementioned irradiation with light.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-1. The results are shown in Table 3.

Example 6-30

Preparation of Anti-Reflection Film

The coating solution for low refraction layer prepared in Example 6-26was applied to the high refraction layer prepared in Example 6-29 usinga gravure coater. The coated material was dried at 80° C., and thenheated to 120° C. for 10 minutes to form a low refraction layer(refractive index: 1.43; thickness: 86 nm). Thus, an anti-reflectionfilm was prepared.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-1. The results are shown in Table 3.

Example 6-31

Preparation of Dispersion of Titanium Dioxide Fine Particles

To 257.1 g of titanium dioxide fine particles (TTO-55B, produced byISHIHARA SANGYO KAISHA, LTD.) were added 38.6 g of the dispersant usedin Example 6-1 and 704.3 g of cyclohexanone. The mixture was subjectedto dispersion using a dynomill to prepare a dispersion of titaniumdioxide fine particles having a weight-average diameter of 70 nm.

(Preparation of Coating Solution for Middle Refraction Layer)

To 85.3 g of the above dispersion of titanium dioxide were added 58.4 gof a mixture of dipentaerythritol pentaacrylate and dipentaerythritolhexaacrylate (DPHA, produced by NIPPON KAYAKU CO., LTD.), 3.1 g of aphotopolymerization initiator (Irgacure 907, produced by CibasophyCiba-Geigy Japan Limited), 1.1 g of a photosensitizer (Kayacure DETX,produced by NIPPON KAYAKU CO., LTD.), 482.4 g of methyl ethyl ketone and1,869.8 g of cyclohexanone. The mixture was then stirred. The mixturewas then filtered through a filter made of polypropylene having a porediameter of 0.4 μm to prepare a coating solution for middle refractionlayer.

Preparation of Coating Solution for High Refraction Layer

To 563.2 g of the above dispersion of titanium dioxide were added 47.9 gof a mixture of dipentaerythritol pentaacrylate and dipentaerythritolhexaacrylate (DPHA, produced by NIPPON KAYAKU CO., LTD.), 4.0 g of aphotopolymerization initiator (Irgacure 907, produced by CibasophyCiba-Geigy Japan Limited), 1.3 g of a photosensitizer (Kayacure DETX,produced by NIPPON KAYAKU CO., LTD.), 455.8 g of methyl ethyl ketone and1,427.8 g of cyclohexanone. The mixture was then stirred. The mixturewas then filtered through a filter made of polypropylene having a porediameter of 0.4 μm to prepare a coating solution for high refractionlayer.

Preparation of Anti-Reflection Film

The coating solution for middle refraction layer was then applied to thehard coat layer prepared in Example 6-1 using a gravure coater. Thecoated material was dried at 100° C., and then irradiated withultraviolet ray having an illuminance of 550 mW/cm² from a 240 W/cmair-cooled metal halide lamp (produced by EYGRAPHICS CO., LTD.) at adose of 600 mJ/cm² while the air in the reaction vessel was being purgedwith nitrogen to an oxygen concentration of not greater than 1.0% byvolume to cause the coat layer to be cured, thereby forming a middlerefraction layer (refractive index: 1.63; thickness: 67 nm).

The coating solution for high refraction layer was then applied to themiddle refraction layer using a gravure coater. The coated material wasdried at 100° C., and then irradiated with ultraviolet ray having anilluminance of 550 mW/cm² from a 240 W/cm air-cooled metal halide lamp(produced by EYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm² while the airin the reaction vessel was being purged with nitrogen to an oxygenconcentration of not greater than 1.0% by volume to cause the coat layerto be cured, thereby forming a high refraction layer (refractive index:1.89; thickness: 108 nm).

The coating solution for low refraction layer prepared in Example 6-25was then applied to the high refraction layer using a gravure coater.The coated material was dried at 80° C., irradiated with ultraviolet rayhaving an illuminance of 550 mW/cm² from a 240 W/cm air-cooled metalhalide lamp (produced by EYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm²while the air in the reaction vessel was being purged with nitrogen toan oxygen concentration of not greater than 1.0% by volume, and thenheated to 120° C. for 10 minutes to form a low refraction layer(refractive index: 1.43; thickness: 86 nm). Thus, an anti-reflectionfilm was prepared. In the middle refraction layer and high refractionlayer, the dispersant was crosslinked and/or polymerized with the binderby the aforementioned irradiation with light.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-1. The results are shown in Table 3.

Example 6-32

Preparation of Dispersion of Titanium Dioxide Fine Particles

A dispersion of titanium dioxide was prepared in the same manner as inExample 6-31 except that the titanium dioxide fine particles of Example6-31 were replaced by MT-500HD (produced by TAYCA CORPORATION).

Preparation of Coating Solution for Middle Refraction Layer

A coating solution for middle refraction layer was prepared in the samemanner as in Example 6-31 except that the above dispersion of titaniumdioxide was used.

Preparation of Coating Solution for High Refraction Layer

A coating solution for high refraction layer was prepared in the samemanner as in Example 6-31 except that the above dispersion of titaniumdioxide was used.

Preparation of Anti-Reflection Film

An anti-reflection film was prepared in the same manner as in Example6-31.

In the middle refraction layer and high refraction layer, the dispersantwas crosslinked and/or polymerized with the binder by the aboveirradiation with light.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-1. The results are shown in Table 3.

Example 6-33

Preparation of Dispersion of Titanium Dioxide Fine Particles

A dispersion of titanium dioxide was prepared in the same manner as inExample 6-31 except that the titanium dioxide fine particles of Example6-31 were replaced by the titanium dioxide fine particles prepared inExample 6-27.

Preparation of Coating Solution for Middle Refraction Layer

A coating solution for middle refraction layer was prepared in the samemanner as in Example 6-31 except that the above dispersion of titaniumdioxide was used.

Preparation of Coating Solution for High Refraction Layer

A coating solution for high refraction layer was prepared in the samemanner as in Example 6-31 except that the above dispersion of titaniumdioxide was used.

Preparation of Anti-Reflection Film

An anti-reflection film was prepared in the same manner as in Example6-31.

In the middle refraction layer and high refraction layer, the dispersantwas crosslinked and/or polymerized with the binder by the aboveirradiation with light.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-1. The results are shown in Table 3.

Example 6-34

Preparation of Dispersion of Titanium Dioxide Fine Particles

A dispersion of titanium dioxide was prepared in the same manner as inExample 6-31 except that the titanium dioxide fine particles of Example6-31 were replaced by the titanium dioxide fine articles prepared inExample 6-29.

Preparation of Coating Solution for Middle Refraction Layer

A coating solution for middle refraction layer was prepared in the samemanner as in Example 6-31 except that the above dispersion of titaniumdioxide was used.

Preparation of Coating Solution for High Refraction Layer

A coating solution for high refraction layer was prepared in the samemanner as in Example 6-31 except that the above dispersion of titaniumdioxide was used.

Preparation of Anti-Reflection Film

An anti-reflection film was prepared in the same manner as in Example6-31.

In the middle refraction layer and high refraction layer, the dispersantwas crosslinked and/or polymerized with the binder by the aforementionedirradiation with light.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-1. The results are shown in Table 3.

Example 6-35

Preparation of Dispersion of Titanium Dioxide Fine Particles

A dispersion of titanium dioxide was prepared in the same manner as inExample 6-31 except that the titanium dioxide fine particles of Example6-31 were replaced by titanium dioxide fine particles containing cobalt(MPT-129, produced by ISHIHARA SANGYOKAISHA, LTD.). MPT-129 is particlescomprising titanium dioxide particles the surface of which have beensubjected to surface treatment (surface treatment with aluminumhydroxide and zirconium hydroxide).

Preparation of Coating Solution for Middle Refraction Layer

A coating solution for middle refraction layer was prepared in the samemanner as in Example 6-31 except that the above dispersion of titaniumdioxide was used.

Preparation of Coating Solution for High Refraction Layer

A coating solution for high refraction layer was prepared in the samemanner as in Example 6-31 except that the above dispersion of titaniumdioxide was used.

Preparation of Anti-Reflection Film

An anti-reflection film was prepared in the same manner as in Example6-31.

In the middle refraction layer and high refraction layer, the dispersantwas crosslinked and/or polymerized with the binder by the aboveirradiation with light.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-1. The results are shown in Table 3.

Comparative Example 3-A

Preparation of Dispersion of Titanium Dioxide Fine Particles

To 250 g of titanium dioxide fine particles (TTO-55B, produced byISHIHARA SANGYO KAISHA, LTD.) were added 37.5 g of the followingdispersant and 712.5 g of cyclohexanone. The mixture was subjected todispersion using a dynomill to prepare a dispersion of titanium dioxidefine particles having a weight-average diameter of 65 nm.

Preparation of Coating Solution for Middle Refraction Layer

To 155.2 g of the above dispersion of titanium dioxide were added 89.5 gof a mixture of dipentaerythritol pentaacrylate and dipentaerythritolhexaacrylate (DPHA, produced by NIPPON KAYAKU CO., LTD.), 4.68 g of aphotopolymerization initiator (Irgacure 907, produced by CibasophyCiba-Geigy Japan Limited), 1.56 g of a photosensitizer (Kayacure DETX,produced by NIPPON KAYAKU CO., LTD.), 770.4 g of methyl ethyl ketone and2,983.0 g of cyclohexanone. The mixture was then stirred. The mixturewas then filtered through a filter made of polypropylene having a porediameter of 0.4 μm to prepare a coating solution for middle refractionlayer.

Preparation of Coating Solution for High Refraction Layer

To 985.7 g of the above dispersion of titanium dioxide were added 48.8 gof a mixture of dipentaerythritol pentaacrylate and dipentaerythritolhexaacrylate (DPHA, produced by NIPPON KAYAKU CO., LTD.), 33.5 g of anacryloyl group-containing silane coupling agent (KBM-5103, produced byShin-Etsu Chemical Co., Ltd.), 4.03 g of a photopolymerization initiator(Irgacure 907, produced by Cibasophy Ciba-Geigy Japan Limited), 1.35 gof a photosensitizer (Kayacure DETX, produced by NIPPON KAYAKU CO.,LTD.), 622.5 g of methyl ethyl ketone and 1,865.0 g of cyclohexanone.The mixture was then stirred. The mixture was then filtered through afilter made of polypropylene having a pore diameter of 0.4 μm to preparea coating solution for high refraction layer.

Preparation of Anti-Reflection Film

The coating solution for middle refraction layer was then applied to thehard coat layer prepared in Example 6-1 using a gravure coater. Thecoated material was dried at 100° C., and then irradiated withultraviolet ray having an illuminance of 550 mW/cm² from a 240 W/cmair-cooled metal halide lamp (produced by EYGRAPHICS CO., LTD.) at adose of 600 mJ/cm² while the air in the reaction vessel was being purgedwith nitrogen to an oxygen concentration of not greater than 1.0% byvolume to cause the coat layer to be cured, thereby forming a middlerefraction layer (refractive index: 1.63; thickness: 67 nm).

The coating solution for high refraction layer was then applied to themiddle refraction layer using a gravure coater. The coated material wasdried at 100° C., and then irradiated with ultraviolet ray having anilluminance of 550 mW/cm² from a 240 W/cm air-cooled metal halide lamp(produced by EYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm² while the airin the reaction vessel was being purged with nitrogen to an oxygenconcentration of not greater than 1.0% by volume to cause the coat layerto be cured, thereby forming a high refraction layer (refractive index:1.90; thickness: 107 nm).

A low refraction film (refractive index: 1.43; thickness: 86 nm) wasthen formed on the high refraction film in the same manner as in Example6-1. Thus, an anti-reflection film was prepared.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-1. The results are shown in Table 3.

Comparative Example 3-B

Preparation of Anti-Reflection Film

A low refraction film (refractive index: 1.43; thickness: 86 nm) wasformed on the high refraction film prepared in Comparative Example 3-Ain the same manner as in Example 6-2. Thus, an anti-reflection film wasprepared.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-1. The results are shown in Table 3.

Comparative Example 3-C

Preparation of Dispersion of Titanium Dioxide Fine Particles

To 250 g of titanium dioxide fine particles (TTO-55B, produced byISHIHARA SANGYO KAISHA, LTD.) were added 37.5 g of the followingdispersant, 2.5 g of a cationic monomer (DMAEA, produced by KOHJIN Co.,Ltd.) and 712.5 g of cyclohexanone. The mixture was subjected todispersion using a dynomill to prepare a dispersion of titanium dioxidefine particles having a weight-average diameter of 65 nm.

Preparation of Coating Solution for Middle Refraction Layer

To 155.2 g of the above dispersion of titanium dioxide were added 89.5 gof a mixture of dipentaerythritol pentaacrylate and dipentaerythritolhexaacrylate (DPHA, produced by NIPPON KAYAKU CO., LTD.), 4.68 g of aphotopolymerization initiator (Irgacure 907, produced by CibasophyCiba-Geigy Japan Limited), 1.56 g of a photosensitizer (Kayacure DETX,produced by NIPPON KAYAKU CO., LTD.), 770.4 g of methyl ethyl ketone and2,983.0 g of cyclohexanone. The mixture was then stirred. The mixturewas then filtered through a filter made of polypropylene having a porediameter of 0.4 μm to prepare a coating solution for middle refractionlayer.

Preparation of Coating Solution for High Refraction Layer

To 985.7 g of the above dispersion of titanium dioxide were added 48.8 gof a mixture of dipentaerythritol pentaacrylate and dipentaerythritolhexaacrylate (DPHA, produced by NIPPON KAYAKU CO., LTD.), 4.03 g of aphotopolymerization initiator (Irgacure 907, produced by CibasophyCiba-Geigy Japan Limited), 1.35 g of a photosensitizer (Kayacure DETX,produced by NIPPON KAYAKU CO., LTD.), 622.5 g of methyl ethyl ketone and1,865.0 g of cyclohexanone. The mixture was then stirred. The mixturewas then filtered through a filter made of polypropylene having a porediameter of 0.4 μm to prepare a coating solution for high refractionlayer.

Preparation of Anti-Reflection Film

The coating solution for middle refraction layer was then applied to thehard coat layer prepared in Example 6-1 using a gravure coater. Thecoated material was dried at 100° C., and then irradiated withultraviolet ray having an illuminance of 550 mW/cm² from a 240 W/cmair-cooled metal halide lamp (produced by EYGRAPHICS CO., LTD.) at adose of 600 mJ/cm² while the air in the reaction vessel was being purgedwith nitrogen to an oxygen concentration of not greater than 1.0% byvolume to cause the coat layer to be cured, thereby forming a middlerefraction layer (refractive index: 1.63; thickness: 67 nm).

The coating solution for high refraction layer was then applied to themiddle refraction layer using a gravure coater. The coated material wasdried at 100° C., and then irradiated with ultraviolet ray having anilluminance of 550 mW/cm² from a 240 W/cm air-cooled metal halide lamp(produced by EYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm² while the airin the reaction vessel was being purged with nitrogen to an oxygenconcentration of not greater than 1.0% by volume to cause the coat layerto be cured, thereby forming a high refraction layer (refractive index:1.90; thickness: 107 nm).

A low refraction film (refractive index: 1.43; thickness: 86 nm) wasthen formed on the high refraction film in the same manner as in Example6-1. Thus, an anti-reflection film was prepared.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-1. The results are shown in Table 3.

Comparative Example 3-D

Preparation of Anti-Reflection Film

A low refraction film (refractive index: 1.43; thickness: 86 nm) wasformed on the high refraction film prepared in Comparative Example 3-Cin the same manner as in Example 6-2. Thus, an anti-reflection film wasprepared.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-1. The results are shown in Table 3.

Comparative Example 3-E

Preparation of Anti-Reflection Film

The anti-reflection film prepared in Example 3-D was subjected toembossing according to the method described in examples inJP-A-2000-329905. Thus, an anti-reflection film having an anti-glareperformance was prepared.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-5. The results are shown in Table 3.

Comparative Example 3-F

Preparation of Coating Solution for Low Refraction Layer

To 180.0 g of monomethyltrimethoxysilane were added 280.0 g of ethanol,440.0 g of 1-butanol, 110.0 g of water and 3.0 g of phosphoric acid. Themixture was then stirred. The mixture was then filtered through a filtermade of polypropylene having a pore diameter of 0.4 μm to prepare acoating solution for low refraction layer.

Preparation of Anti-Reflection Film

The coating solution for low refraction layer was applied to the highrefraction layer prepared in Comparative Example 3-C using a gravurecoater. The coated material was dried at 80° C., and then heated to 120°C. for 24 hours to form a low refraction layer (refractive index: 1.46;thickness: 86 nm). Thus, an anti-reflection film was prepared.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-1. The results are shown in Table 3.

Comparative Example 3-G

Preparation of Coating Solution for Low Refraction Layer

A commercially available coating composition for low refraction layer(Cytop CTL-102AP, produced by ASAHI GLASS COMPANY) was applied to thehigh refraction layer prepared in Comparative Example 3-C using agravure coater. The coated material was dried at 80° C., and then heatedto 120° C. for 10 minutes to form a low refraction layer (thickness: 86nm). Thus, an anti-reflection film was prepared.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-1. The results are shown in Table 3.

Comparative Example 3-H

Preparation of Dispersion of Titanium Dioxide Fine Particles

To 250 g of titanium dioxide fine particles (TTO-55N, produced byISHIHARA SANGYO KAISHA, LTD.) were added 37.5 g of the dispersant usedin Comparative Example 3-C, 2.5 g of a cationic monomer (DMAEA, producedby KOHJIN Co., Ltd.) and 710 g of cyclohexanone. The mixture was thensubjected to dispersion using a dynomill to prepare a dispersion oftitanium dioxide having a weight-average diameter of 65 nm.

Preparation of Coating Solution for Middle Refraction Layer

To 155.2 g of the above dispersion of titanium dioxide were added 89.5 gof a mixture of dipentaerythritol pentaacrylate and dipentaerythritolhexaacrylate (DPHA, produced by NIPPON KAYAKU CO., LTD.), 4.68 g of aphotopolymerization initiator (Irgacure 907, produced by CibasophyCiba-Geigy Japan Limited), 1.56 g of a photosensitizer (Kayacure DETX,produced by NIPPON KAYAKU CO., LTD.), 770.4 g of methyl ethyl ketone and2,983.0 g of cyclohexanone. The mixture was then stirred. The mixturewas then filtered through a filter made of polypropylene having a porediameter of 0.4 μm to prepare a coating solution for middle refractionlayer.

Preparation of Coating Solution for High Refraction Layer

To 985.7 g of the above dispersion of titanium dioxide were added 48.8 gof a mixture of dipentaerythritol pentaacrylate and dipentaerythritolhexaacrylate (DPHA, produced by NIPPON KAYAKU CO., LTD.), 4.03 g of aphotopolymerization initiator (Irgacure 907, produced by CibasophyCiba-Geigy Japan Limited), 1.35 g of a photosensitizer (Kayacure DETX,produced by NIPPON KAYAKU CO., LTD.), 622.5 g of methyl ethyl ketone and1,865.0 g of cyclohexanone. The mixture was then stirred. The mixturewas then filtered through a filter made of polypropylene having a porediameter of 0.4 μm to prepare a coating solution for high refractionlayer.

Preparation of Anti-Reflection Film

The coating solution for middle refraction layer was then applied to thehard coat layer prepared in Example 6-1 using a gravure coater. Thecoated material was dried at 100° C., and then irradiated withultraviolet ray having an illuminance of 550 mW/cm² from a 240 W/cmair-cooled metal halide lamp (produced by EYGRAPHICS CO., LTD.) at adose of 600 mJ/cm² while the air in the reaction vessel was being purgedwith nitrogen to an oxygen concentration of not greater than 1.0% byvolume to cause the coat layer to be cured, thereby forming a middlerefraction layer (refractive index: 1.64; thickness: 67 nm).

The coating solution for high refraction layer was then applied to themiddle refraction layer using a gravure coater. The coated material wasdried at 100° C., and then irradiated with ultraviolet ray having anilluminance of 550 mW/cm² from a 240 W/cm air-cooled metal halide lamp(produced by EYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm² while the airin the reaction vessel was being purged with nitrogen to an oxygenconcentration of not greater than 1.0% by volume to cause the coat layerto be cured, thereby forming a high refraction layer (refractive index:1.91; thickness: 107 nm).

A low refraction film (refractive index: 1.43; thickness: 86 nm) wasthen formed on the high refraction film in the same manner as in Example6-25. Thus, an anti-reflection film was prepared.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-1. The results are shown in Table 3.

Comparative Example 3-I

Preparation of Anti-Reflection Film

A low refraction film (refractive index: 1.43; thickness: 86 nm) wasformed on the high refraction film prepared in Comparative Example 3-Hin the same manner as in Example 6-26. Thus, an anti-reflection film wasprepared.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was evaluated in the same manneras in Example 6-1. The results are shown in Table 3.

Comparative Example 3-J

Preparation of Dispersion of Titanium Dioxide Fine Particles

To 257.1 g of titanium dioxide fine particles (TTO-55N, produced byISHIHARA SANGYO KAISHA, LTD.) were added 38.6 g of the dispersant usedin Comparative Example 1-C, 2.6 g of a cationic monomer (DMAEA, producedby KOHJIN Co., Ltd.) and 701.7 g of cyclohexanone. The mixture was thensubjected to dispersion using a dynomill to prepare a dispersion oftitanium dioxide having a weight-average diameter of 70 nm.

Preparation of Coating Solution for Middle Refraction Layer

A coating solution for middle refraction layer was prepared in the samemanner as in Example 6-31 except that the above dispersion of titaniumdioxide was used.

Preparation of Coating Solution for High Refraction Layer

A coating solution for high refraction layer was prepared in the samemanner as in Example 6-31 except that the above dispersion of titaniumdioxide was used.

Preparation of Anti-Reflection Film

An anti-reflection film was prepared in the same manner as in Example6-31.

Evaluation of Anti-Reflection Film

The anti-reflection film thus prepared was then evaluated in the samemanner as in Example 6-1. The results are shown in Table 3.

Example 6-36

Preparation of Anti-Reflection Film

An anti-reflection film was prepared in the same manner as in Example6-1 except that the following hard coat layer having a thickness of 8 μmwas provided in place of the hard coat layer of Example 6-1.

Preparation of Composition for Hard Coat Layer

1,296 g of trimethylolpropane triacrylate and 809 g of a 53.2 mass %methyl ethyl ketone solution of polygcidyl methacrylate (mass averagemolecular weight: 1.5×10⁴) were dissolved in a mixed solution of 943 gof methyl ethyl ketone and 880 g of cyclohexane. 184.48 g of Irgacureand 24 g of di(t-butylphenyl iodonium hexafluorophosphate) were added tothe solution while stirring, and the resulting mixture was stirred for10 minutes. The mixture was filtered through a filter made ofpolypropylene having a pore size of 0.5 μm to prepare a composition forhard coat layer.

Preparation of Hard Coat Layer

The coating composition obtained above was applied to the highreflection layer using a bar coater. After drying at 80° C. for 2minutes, the coating film was irradiated with ultraviolet ray of 500mJ/cm² while purging with nitrogen gas so as to maintain an atmospheresuch that oxygen concentration was 1.0 vol % or less. Thus, a hard coatlayer having a thickness of 8 μm was formed.

Performance of the anti-reflection film thus obtained was evaluated inthe same manner as in Example 6-1. As a result, the same good results asin Example 6-1 were obtained.

Example 7-1

Preparation of Saponified Transparent Support

A 1.5 N aqueous solution of sodium hydroxide was prepared, and thenkept. at 50° C. A 0.01 N diluted aqueous solution of sulfuric acid.

A triacetyl cellulose film having a thickness of 80 μm (TAC-TD80UF,produced by Fuji Photo Film Co., Ltd.) was dipped in the aforementionedaqueous solution of sodium hydroxide for 2 minutes, and then dipped inwater so that the aqueous solution of sodium hydroxide was thoroughlywashed away. Subsequently, the triacetyl cellulose film was dipped inthe aforementioned diluted aqueous solution of sulfuric acid for 1minute, dipped in water so that the diluted aqueous solution of sulfuricacid was thoroughly washed away, and then thoroughly dried at 100° C.

The triacetyl cellulose film thus saponified was then evaluated forcontact angle with respect to water on the surface thereof. As a result,the contact angle was not greater than 40 degrees on the both surfacesthereof.

Thus, a saponified transparent support was prepared.

Preparation of Protective Film for Polarizing Plate

Using a corona discharge treatment machine produced by Vetaphone Inc. ofDenmark, the saponified transparent support was subjected to coronadischarge treatment on one side thereof.

Subsequently, on the corona-discharged side of the saponifiedtransparent support were applied a hard coat layer, a middle refractionlayer, a high refraction layer and a low refraction layer in the samemanner as in Example 6-1 to prepare a protective film for polarizingplate.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was evaluated inthe same manner as in Example 6-1. The results are shown in Table 4.

Example 7-2

Preparation of Protective Film for Polarizing Plate

Using a corona discharge treatment machine produced by Vetaphone Inc. ofDenmark, the saponified transparent support prepared in Example 7-1 wassubjected to corona discharge treatment on one side thereof.

Subsequently, on the corona-discharged side of the saponifiedtransparent support were applied a hard coat layer, a middle refractionlayer, a high refraction layer and a low refraction layer in the samemanner as in Example 6-2 to prepare a protective film for polarizingplate.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was evaluated inthe same manner as in Example 6-1. The results are shown in Table 4.

Example 7-3

Preparation of Protective Film for Polarizing Plate

Using a corona discharge treatment machine produced by Vetaphone Inc. ofDenmark, the saponified transparent support prepared in Example 7-1 wassubjected to corona discharge treatment on one side thereof.

Subsequently, on the corona-discharged side of the saponifiedtransparent support were applied a hard coat layer, a middle refractionlayer, a high refraction layer and a low refraction layer in the samemanner as in Example 6-13 to prepare a protective film for polarizingplate.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was evaluated inthe same manner as in Example 6-1. The results are shown in Table 4.

Example 7-4

Preparation of Protective Film for Polarizing Plate

Using a corona discharge treatment machine produced by Vetaphone Inc. ofDenmark, the saponified transparent support prepared in Example 7-1 wassubjected to corona discharge treatment on one side thereof.

Subsequently, on the corona-discharged side of the saponifiedtransparent support were applied a hard coat layer, a middle refractionlayer, a high refraction layer and a low refraction layer in the samemanner as in Example 6-14 to prepare a protective film for polarizingplate.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was evaluated inthe same manner as in Example 6-1. The results are shown in Table 4.

Example 7-5

Preparation of Protective Film for Polarizing Plate

Using a corona discharge treatment machine produced by Vetaphone Inc. ofDenmark, the saponified transparent support prepared in Example 7-1 wassubjected to corona discharge treatment on one side thereof.

Subsequently, on the corona-discharged side of the saponifiedtransparent support were applied a hard coat layer, a middle refractionlayer, a high refraction layer and a low refraction layer in the samemanner as in Example 6-21 to prepare a protective film for polarizingplate.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was evaluated inthe same manner as in Example 6-5. The results are shown in Table 4.

Example 7-6

Preparation of Protective Film for Polarizing Plate

Using a corona discharge treatment machine produced by Vetaphone Inc. ofDenmark, the saponified transparent support prepared in Example 7-1 wassubjected to corona discharge treatment on one side thereof.

Subsequently, on the corona-discharged side of the saponifiedtransparent support were applied a hard coat layer, a middle refractionlayer, a high refraction layer and a low refraction layer in the samemanner as in Example 6-22 to prepare a protective film for polarizingplate.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was evaluated inthe same manner as in Example 6-5. The results are shown in Table 4.

Example 7-7

Preparation of Saponified Transparent Support

A 1.5 N aqueous solution of sodium hydroxide was prepared, and then keptat 50° C. A 0.01 N diluted aqueous solution of sulfuric acid.

The anti-reflection film prepared in Example 6-1 was dipped in the aboveaqueous solution of sodium hydroxide for 2 minutes, and then dipped inwater so that the aqueous solution of sodium hydroxide was thoroughlywashed away. Subsequently, the anti-reflection film was dipped in theaforementioned diluted aqueous solution of sulfuric acid for 1 minute,dipped in water so that the diluted aqueous solution of sulfuric acidwas thoroughly washed away, and then thoroughly dried at 100° C.

The anti-reflection film thus saponified was then evaluated for contactangle with respect to water on the surface of the transparent support onthe side thereof opposite the side having a high refraction film. As aresult, the contact angle was not greater than 40 degrees. Thus, asaponified transparent support was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated for film exfoliation due to saponification.

The protective film for polarizing plate was further evaluated in thesame manner as in Example 6-1. The results are shown in Table 4.

(1) Evaluation of Film Exfoliation Due to Saponification

100 sheets of the anti-reflection film were subjected to saponification.These sheets of anti-reflection film were each then visually observedfor the occurrence of film exfoliation. The results were then evaluatedaccording to the following 3-step criterion.

-   -   G: None of 100 sheets observed exfoliated    -   F: 5 or less out of 100 sheets observed exfoliated    -   P: More than 5 out of 100 sheets observed exfoliated

Example 7-8

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in Example 6-2 was subjected tosaponification in the same manner as in Example 7-7. Thus, a protectivefilm for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-7. The results are shown inTable 4.

Example 7-9

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in Example 6-5 was subjected tosaponification in the same manner as in Example 7-7. Thus, a protectivefilm for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated for film exfoliation due to saponification in the same manneras in Example 7-7. The protective film for polarizing plate thusprepared was then evaluated in the same manner as in Example 6-5. Theresults are shown in Table 4.

Example 7-10

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in Example 6-6 was subjected tosaponification in the same manner as in Example 7-7. Thus, a protectivefilm for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-9. The results are shown inTable 4.

Example 7-11

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in Example 6-7 was subjected tosaponification in the same manner as in Example 7-7. Thus, a protectivefilm for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-7. The results are shown inTable 4.

Example 7-12

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in Example 6-8 was subjected tosaponification in the same manner as in Example 7-7. Thus, a protectivefilm for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-7. The results are shown inTable 4.

Example 7-13

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in Example 6-9 was subjected tosaponification in the same manner as in Example 7-7. Thus, a protectivefilm for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-7. The results are shown inTable 4.

Example 7-14

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in Example 6-10 was subjected tosaponification in the same manner as in Example 7-7. Thus, a protectivefilm for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-7. The results are shown inTable 4.

Example 7-15

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in Example 6-11 was subjected tosaponification in the same manner as in Example 7-7. Thus, a protectivefilm for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-9. The results are shown inTable 4.

Example 7-16

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in Example 6-12 was subjected tosaponification in the same manner as in Example 7-7. Thus, a protectivefilm for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-9. The results are shown inTable 4.

Example 7-17

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in Example 6-13 was subjected tosaponification in the same manner as in Example 7-7. Thus, a protectivefilm for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-7. The results are shown inTable 4.

Example 7-18

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in Example 6-14 was subjected tosaponification in the same manner as in Example 7-7. Thus, a protectivefilm for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-7. The results are shown inTable 4.

Example 7-19

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in Example 6-15 was subjected tosaponification in the same manner as in Example 7-7. Thus, a protectivefilm for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-7. The results are shown inTable 4.

Example 7-20

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in Example 6-16 was subjected tosaponification in the same manner as in Example 7-7. Thus, a protectivefilm for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-7. The results are shown inTable 4.

Example 7-21

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in Example 6-17 was subjected tosaponification in the same manner as in Example 7-7. Thus, a protectivefilm for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-7. The results are shown inTable 4.

Example 7-22

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in Example 6-18 was subjected tosaponification in the same manner as in Example 7-7. Thus, a protectivefilm for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-7. The results are shown inTable 4.

Example 7-23

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in Example 6-19 was subjected tosaponification in the same manner as in Example 7-7. Thus, a protectivefilm for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-7. The results are shown inTable 4.

Example 7-24

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in Example 6-20 was subjected tosaponification in the same manner as in Example 7-7. Thus, a protectivefilm for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-7. The results are shown inTable 4.

Example 7-25

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in Example 6-21 was subjected tosaponification in the same manner as in Example 7-7. Thus, a protectivefilm for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-9. The results are shown inTable 4.

Example 7-26

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in Example 6-22 was subjected tosaponification in the same manner as in Example 7-7. Thus, a protectivefilm for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-9. The results are shown inTable 4.

Example 7-27

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in Example 6-23 was subjected tosaponification in the same manner as in Example 7-7. Thus, a protectivefilm for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-9. The results are shown inTable 4.

Example 7-28

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in Example 6-24 was subjected tosaponification in the same manner as in Example 7-7. Thus, a protectivefilm for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-9. The results are shown inTable 4.

Example 7-29

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in Example 6-25 was subjected tosaponification in the same manner as in Example 7-7. Thus, a protectivefilm for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-7. The results are shown inTable 4.

Example 7-30

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in Example 6-26 was subjected tosaponification in the same manner as in Example 7-7. Thus, a protectivefilm for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-7. The results are shown inTable 4.

Example 7-31

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in Example 6-27 was subjected tosaponification in the same manner as in Example 7-7. Thus, a protectivefilm for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-7. The results are shown inTable 4.

Example 7-32

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in Example 6-28 was subjected tosaponification in the same manner as in Example 7-7. Thus, a protectivefilm for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-7. The results are shown inTable 4.

Example 7-33

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in Example 6-29 was subjected tosaponification in the same manner as in Example 7-7. Thus, a protectivefilm for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-7. The results are shown inTable 4.

Example 7-34

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in Example 6-30 was subjected tosaponification in the same manner as in Example 7-7. Thus, a protectivefilm for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-7. The results are shown inTable 4.

Example 7-35

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in Example 6-31 was subjected tosaponification in the same manner as in Example 7-7. Thus, a protectivefilm for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-7. The results are shown inTable 4.

Example 7-36

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in Example 6-32 was subjected tosaponification in the same manner as in Example 7-7. Thus, a protectivefilm for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-7. The results are shown inTable 4.

Example 7-37

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in Example 6-33 was subjected tosaponification in the same manner as in Example 7-7. Thus, a protectivefilm for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-7. The results are shown inTable 4.

Example 7-38

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in Example 6-34 was subjected tosaponification in the same manner as in Example 7-7. Thus, a protectivefilm for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-7. The results are shown inTable 4.

Example 7-39

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in Example 6-35 was subjected tosaponification in the same manner as in Example 2-7. Thus, a protectivefilm for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-7. The results are shown inTable 4.

Comparative Example 4-A

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in comparative Example 3-A wassubjected to saponification in the same manner as in Example 7-7. Thus,a protective film for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-7. The results are shown inTable 4.

Comparative Example 4-B

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in comparative Example 3-B wassubjected to saponification in the same manner as in Example 7-7. Thus,a protective film for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-7. The results are shown inTable 4.

Comparative Example 4-C

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in comparative Example 3-C wassubjected to saponification in the same manner as in Example 7-7. Thus,a protective film for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-7. The results are shown inTable 4.

Comparative Example 4-D

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in comparative Example 3-D wassubjected to saponification in the same manner as in Example 7-7. Thus,a protective film for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-7. The results are shown inTable 4.

Comparative Example 4-E

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in comparative Example 3-E wassubjected to saponification in the same manner as in Example 7-7. Thus,a protective film for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-9. The results are shown inTable 4.

Comparative Example 4-F

Preparation of Protective Film for Polarizing Plate

An anti-reflection film was prepared in the same manner as inComparative Example 3-D except that nitrogen purge was not effect duringthe preparation of the middle refraction layer and the high refractionlayer.

The anti-reflection film thus prepared was subjected to saponificationin the same manner as in Example 7-7. Thus, a protective film forpolarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-7. The results are shown inTable 4.

Comparative Example 4-G

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in comparative Example 3-H wassubjected to saponification in the same manner as in Example 7-7. Thus,a protective film for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-7. The results are shown inTable 4.

Comparative Example 4-H

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in comparative Example 3-I wassubjected to saponification in the same manner as in Example 7-7. Thus,a protective film for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-7. The results are shown inTable 4.

Comparative Example 4-I

Preparation of Protective Film for Polarizing Plate

The anti-reflection film prepared in comparative Example 3-J wassubjected to saponification in the same manner as in Example 7-7. Thus,a protective film for polarizing plate was prepared.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-7. The results are shown inTable 4.

TABLE 4 Resistance to Dynamic Finger Magic Checker- Anti- Film scratchPencil firction print ink Contact board glare Light-resistance exfoli-with steel hard- coef- Chemical wipa- wipa- angle adhesive- Ra perfor-Hours ation wool ness ficient ressitance bility bility (°) ness (μm)mace 100 200 300 Example 7-1 — E 3H 0.10 G G G 102 E — — — — — Example7-2 — E 3H 0.09 G G G 103 E — — — — — Example 7-3 — E 3H 0.10 G G G 102E — — — — — Example 7-4 — G 3H 0.09 G G G 103 E — — — — — Example 7-5 —E 3H 0.11 G G G 102 E 0.13 E — — — Example 7-6 — G 3H 0.11 G G G 102 E0.13 E — — — Example 7-7 G E 3H 0.13 G G G 102 E — — — — — Example 7-8 GE 3H 0.12 G G G 101 E — — — — — Example 7-9 G E 3H 0.13 G G G 101 E 0.06G — — — Example 7-10 G E 3H 0.13 G G G 100 E 0.06 G — — — Example 7-11 GE 3H 0.12 G G G 101 E — — — — — Example 7-12 G G 3H 0.11 G G G 101 E — —— — — Example 7-13 G E 3H 0.13 G G G 102 E — — — — — Example 7-14 G E 3H0.12 G G G 101 E — — — — — Example 7-15 G E 3H 0.13 G G G 100 E 0.07 G —— — Example 7-16 G E 3H 0.13 G G G 102 E 0.06 G — — — Example 7-17 G E3H 0.12 G G G 102 E — — — — — Example 7-18 G G 3H 0.12 G G G 101 E — — —— — Example 7-19 G E 3H 0.12 G G G 101 E — — — — — Example 7-20 G E 3H0.12 G G G 101 E — — — — — Example 7-21 G E 3H 0.13 G G G 103 E — — — —— Example 7-22 G E 3H 0.12 G G G 101 E — — — — — Example 7-23 G E 3H0.13 G G G 101 E — — — — — Example 7-24 G E 3H 0.12 G G G 102 E — — — —— Example 7-25 G E 3H 0.13 G G G 101 E 0.13 E — — — Example 7-26 G G 3H0.13 G G G 101 E 0.13 E — — — Example 7-27 G E 3H 0.12 G G G 102 E 0.12E — — — Example 7-28 G G 3H 0.13 G G G 102 E 0.12 E — — — Example 7-29 GE 3H 0.12 G G G 101 E — — — — — Example 7-30 G E 3H 0.13 G G G 100 E — —— — — Example 7-31 G E 3H 0.12 G G G 102 E — — — — — Example 7-32 G E 3H0.13 G G G 100 E — — — — — Example 7-33 G E 3H 0.12 G G G 101 E — — — —— Example 7-34 G E 3H 0.13 G G G 100 E — — — — — Example 7-35 G E 3H0.12 G G G 101 E — — F P P Example 7-36 G E 3H 0.11 G G G 102 E — — G PP Example 7-37 G E 3H 0.12 G G G 101 E — — E G F Example 7-38 G E 3H0.12 G G G 102 E — — E G F Example 7-39 G E 3H 0.12 G G G 101 E — — E GF Comparative G F 2H 0.13 P G P 100 E — — — — — Example 4-A ComparativeG F 2H 0.12 P G P 101 E — — — — — Example 4-B Comparative G P 3H 0.12 PG P 101 E — — — — — Example 4-C Comparative G P 3H 0.11 P G P 101 E — —— — — Example 4-D Comparative G P 3H 0.13 P G P 102 E 0.06 G — — —Example 4-E Comparative P — — — — — — — E — — — — — Example 4-FComparative G P 3H 0.12 P G P 101 E — — — — — Example 4-G Comparative GP 3H 0.13 P G P 100 E — — — — — Example 4-H Comparative G P 3H 0.12 P GP 102 E — — P P P Example 4-I

Example 8

Preparation of Protective Film for Polarizing Plate

A 1.5 N aqueous solution of sodium hydroxide was prepared, and then keptat 35° C. A 0.01 N diluted aqueous solution of sulfuric acid.

A protective film for polarizing plate was prepared in the same manneras in Example 7 except that the time during which the film is dipped inthe aqueous solution of sodium hydroxide was properly adjusted such thatthe transparent support exhibited a contact angle of 35 degrees withrespect to water on the side thereof opposite the side having a highrefraction film.

Evaluation of Protective Film for Polarizing Plate

The protective film for polarizing plate thus prepared was thenevaluated in the same manner as in Example 7-7 and 7-9. The results areshown in Table 5.

TABLE 5 Resistance to Dynamic Finger Magic Checker- Anti- Film scratchPencil firction print ink Contact board glare Light-resistance exfoli-with steel hard- coef- Chemical wipa- wipa- angle adhesive- Ra perfor-Hours ation wool ness ficient ressitance bility bility (°) ness (μm)mace 100 200 300 Example 8-1 — E 3H 0.09 G G G 103 E — — E G F Example8-2 — E 3H 0.10 G G G 103 E — — E G F Example 8-3 — E 3H 0.09 G G G 103E — — E G F Example 8-4 — G 3H 0.10 G G G 104 E — — E G F Example 8-5 —E 3H 0.10 G G G 103 E 0.13 E E G F Example 8-6 — G 3H 0.10 G G G 102 E0.13 E E G F Example 8-7 G E 3H 0.12 G G G 103 E — — E G F Example 8-8 GE 3H 0.11 G G G 102 E — — E G F Example 8-9 G E 3H 0.12 G G G 101 E 0.06G E G F Example 8-10 G E 3H 0.12 G G G 101 E 0.06 G E G F Example 8-11 GE 3H 0.11 G G G 101 E — — E G F Example 8-12 G G 3H 0.10 G G G 102 E — —E G F Example 8-13 G E 3H 0.12 G G G 102 E — — E G F Example 8-14 G E 3H0.11 G G G 102 E — — E G F Example 8-15 G E 3H 0.12 G G G 102 E 0.07 G EG F Example 8-16 G E 3H 0.12 G G G 102 E 0.06 G E G F Example 8-17 G E3H 0.11 G G G 102 E — — E G F Example 8-18 G G 3H 0.11 G G G 101 E — — EG F Example 8-19 G E 3H 0.11 G G G 102 E — — E G F Example 8-20 G E 3H0.11 G G G 103 E — — E G F Example 8-21 G E 3H 0.12 G G G 103 E — — E GF Example 8-22 G E 3H 0.11 G G G 101 E — — E G F Example 8-23 G E 3H0.12 G G G 102 E — — E G F Example 8-24 G E 3H 0.11 G G G 102 E — — E GF Example 8-24 G E 3H 0.11 G G G 102 E — — E G F Example 8-25 G E 3H0.12 G G G 103 E 0.13 E E G F Example 8-26 G G 3H 0.12 G G G 101 E 0.13E E G F Example 8-27 G E 3H 0.11 G G G 103 E 0.12 E E G F Example 8-28 GG 3H 0.12 G G G 102 E 0.12 E E G F Example 8-29 G E 3H 0.11 G G G 102 E— — E G F Example 8-30 G E 3H 0.12 G G G 101 E — — E G F Example 8-31 GE 3H 0.11 G G G 103 E — — E E G Example 8-32 G E 3H 0.12 G G G 103 E — —E E G Example 8-33 G E 3H 0.11 G G G 102 E — — E E E Example 8-34 G E 3H0.12 G G G 101 E — — E E E Example 8-35 G E 3H 0.10 G G G 103 E — — E GF Example 8-36 G E 3H 0.11 G G G 102 E — — E G F Example 8-37 G E 3H0.10 G G G 103 E — — E E G Example 8-38 G E 3H 0.11 G G G 102 E — — E EE Example 8-39 G E 3H 0.10 G G G 103 E — — E E E Comparative G F 2H 0.12G G G 103 E — — E G F Example 5-A Comparative G F 2H 0.11 G G G 102 E —— E G F Example 5-B Comparative G P 3H 0.11 G G G 101 E — — E G FExample 5-C Comparative G P 3H 0.10 G G G 102 E — — E G F Example 5-DComparative G P 3H 0.12 G G G 103 E 0.06 G E G F Example 5-E ComparativeP — — — G G G 103 E — — — — — Example 5-F Comparative G P 3H 0.11 G G G101 E — — P P P Example 5-G Comparative G P 3H 0.12 G G G 103 E — — P PP Example 5-H Comparative G P 3H 0.12 G G G 102 E — — P P P Example 5-I

Example 9

Preparation of Transparent Support

A heterogeneous gel-like solution obtained by mixing and stirring 20parts by weight of triacetyl cellulose, 48 parts by weight of methylacetate, 20 parts by weight of cyclohexanone, 5 parts by weight ofmethanol, 5 parts by weight of ethanol, 2 parts by weight of triphenylphosphate/biphenyldiphenyl phosphate (1/2), 0.1 parts by weight ofsilica (particle diameter: 20 nm) and 0.2 parts by weight of2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazinewas cooled to −70° C. for 6 hours, and then heated to 50° C. withstirring to prepare a triacetyl cellulose dope A.

The above triacetyl cellulose dope A was subjected to single-layer drumcasting according to JP-A-7-11055 to prepare a triacetyl cellulose filmhaving a thickness of 80 μm. Thus, a transparent support was prepared.

Preparation and Evaluation of Anti-Reflection Film and Protective Filmfor Polarizing Plate

The testing procedure of Examples 6 to 8 were followed except that thetransparent support thus prepared was used. The results weresubstantially the same as in Examples 6 to 8.

Example 10

Preparation of Transparent Support

The triacetyl cellulose dope A of Example 9 was heated to 180° C. at 1MPa in a stainless steel sealable vessel for 5 minutes. The sealedvessel was then put in a 50° C. water bath to prepare a triacetylcellulose dope B.

The above triacetyl cellulose dope B was then subjected to single-layerdrum casting according to JP-A-7-11055to prepare a triacetyl cellulosefilm having a thickness of 40 μm. Thus, a transparent support wasprepared.

Preparation and Evaluation of Anti-Reflection Film and Protective Filmfor Polarizing Plate

The testing procedure of Example 9 was followed except that thetransparent support thus prepared was used. The results weresubstantially the same as in Example 9.

Example 11

Preparation of Polarizing Plate

A polyvinyl alcohol film having a thickness of 75 μm (produced byKURARAY CO., LTD.) was dipped in an aqueous solution comprising 100parts by weight of water, 7 parts by weight of iodine and 105 parts byweight of potassium iodide so that iodine was adsorbed thereto.Subsequently, this film was longitudinally monoaxially stretched by afactor of 4.4 in a 4 wt % aqueous solution of boric acid, and then driedwhile being tensed to prepare a polarizing plate.

The protective films for polarizing plate described in Examples 7 to 10were each then adhered to one side of the polarizing plate with apolyvinyl alcohol-based adhesive as an adhesive in such an arrangementthat the saponified triacetyl cellulose side thereof was opposed to thepolarizing plate. Further, a triacetyl cellulose film which had beensaponified in the same manner as in Example 7-1 was adhered to the otherside of the polarizing plate with the same polyvinyl alcohol-basedadhesive. Thus, polarizing plates of the present invention wereprepared.

For comparison, a protective film for polarizing plate having a contactangle of greater than 40 degrees with respect to water on the sidethereof opposed to the polarizing plate was prepared by properlyadjusting the saponification time. This protective film for polarizingplate was then processed in the same manner as mentioned above toprepare a polarizing plate.

Evaluation of Polarizing plate and Results of Evaluation

The polarizing plates thus prepared were each then evaluated for thefollowing properties.

(1) Punching Test

The polarizing plates thus prepared were each subjected to punching testby which it is punched to a size of 26 in. by 100 sheets using adumbbell die. The presence or absence of exfoliation of the polarizingfilm from the protective film for polarizing plate was then observed.

(2) Durability Test

100 sheets of the polarizing plate which had not been observedexfoliated in the punching test were allowed to stand in athermo-hygrostat of 70° C. and 93% RH and a thermo-hygrostat of 25° C.and 93% RH alternately for 12 hours, totaling 100 hours, to undergodurability test. The test specimens were then observed for exfoliationof protective film from polarizing film.

None of 100 sheets of the polarizing plates prepared from the protectivefilms for polarizing plate of the present invention having a contactangle of not greater than 40 degrees with respect to water on the sidethereof opposed to the polarizing film were observed exfoliated betweenthe polarizing film and the protective film for polarizing plate in thepunching test and the durability test.

On the other hand, 5 or more of 100 sheets of the protective films forpolarizing plate having a contact angle of greater than 40 degrees withrespect to water on the side thereof opposite the polarizing film wereobserved exfoliated between the polarizing film and the protective filmfor polarizing plate in the punching test and the durability test.

Example 12

An optically anisotropic optically-compensated film having a disc ofdiscotic structural unit disposed oblique to the surface of thetransparent support which changes in its angle between the disc ofdiscotic structural unit and the surface of the transparent support withthe distance from the transparent support (Wide View Film SA-12B,produced by Fuji Photo Film Co., Ltd.) was subjected to saponificationon the side thereof opposite the side having an optically anisotropiclayer under the same conditions as in Example 7-7.

The protective films for polarizing plate of the present inventionprepared in Examples 7 to 10 were each then adhered to one side of thepolarizing film prepared in Example 6 with a polyvinyl alcohol-basedadhesive as an adhesive in such an arrangement that the saponifiedtriacetyl cellulose side thereof was opposed to the polarizing film.Further, the saponified optically compensated film was adhered to theother side of the polarizing film with the same polyvinyl alcohol-basedadhesive in such an arrangement that the triacetyl cellulose sidethereof was opposed to the polarizing film. TN, STN, IPS, VA and OCBmode transmission type, reflection type or semi-transmission type liquidcrystal display devices provided with the polarizing plate of thepresent invention thus prepared exhibited an excellent daylightcontrast, a very wide vertical and horizontal angle of view, anextremely excellent visibility and an excellent display quality ascompared with liquid crystal display devices provided with a polarizingplate free of optically compensated film.

Example 13

Preparation of Coating Solution for Hard Coat Layer

To 315.0 g of a mixture of dipentaerythritol pentaacrylate anddipentaerythritol hexaacrylate (DPHA, produced by NIPPON KAYAKU CO.,LTD.) were added 450.0 g of a methyl ethyl ketone dispersion of silicafine particles (MEK-ST, solid content concentration: 30% by weight,produced by NISSAN CHEMICAL INDUSTRIES, LTD.), 15.0 g of methyl ethylketone, 220.0 g of cyclohexanone and 16.0 g of a photopolymerizationinitiator (Irgacure 907, produced by Cibasophy Ciba-Geigy JapanLimited). The mixture was then stirred. The mixture was then filteredthrough a filter made of polypropylene having a pore diameter of 0.4 μmto prepare a coating solution for hard coat layer.

Preparation of Dispersion of Titanium Dioxide Fine Particles

As titanium dioxide fine particles there were used cobalt-containingtitanium dioxide fine particles (MPT-129, produced by ISHIHARA SANGYOKAISHA, LTD.) which had been subjected to surface treatment withaluminum hydroxide and zirconium hydroxide.

To 257.1 g of the fine particles were then added 38.6 g of the followingdispersant and 704.3 g of cyclohexanone. The mixture was then subjectedto dispersion using a dynomill to prepare a dispersion of titaniumdioxide having a weight-average diameter of 70 nm.

Preparation of Coating Solution A for Middle Refraction Layer

To 88.9 g of the aforementioned dispersion of titanium dioxide wereadded 58.4 g of a mixture of dipentaerythritol pentaacrylate anddipentaerythritol hexaacrylate (DPHA), 3.1 g of a photopolymerizationinitiator (Irgacure 907, produced by Cibasophy Ciba-Geigy JapanLimited), 1.1 g of a photosensitizer (Kayacure DETX, produced by NIPPONKAYAKU CO., LTD.), 482.4 g of methyl ethyl ketone and 1,869.8 g ofcyclohexanone. The mixture was then stirred. The mixture was thenfiltered through a filter made of polypropylene having a pore diameterof 0.4 μm to prepare a coating solution for middle refraction layer.

Preparation of Coating Solution A for High Refraction Layer

To 586.8 g of the aforementioned dispersion A of titanium dioxide wereadded 47.9 g of a mixture of dipentaerythritol pentaacrylate anddipentaerythritol hexaacrylate (DPHA, produced by NIPPON KAYAKU CO.,LTD.), 4.0 g of a photopolymerization initiator (Irgacure 907, producedby Cibasophy Ciba-Geigy Japan Limited), 1.3 g of a photosensitizer(Kayacure DETX, produced by NIPPON KAYAKU CO., LTD.), 455.8 g of methylethyl ketone and 1,427.8 g of cyclohexanone. The mixture was thenstirred. The mixture was then filtered through a filter made ofpolypropylene having a pore diameter of 0.4 μm to prepare a coatingsolution for high refraction layer.

Preparation of Silane Compound

In a reaction vessel equipped with an agitator and a reflux condenserwere charged and mixed 161 parts by weight of3-acryloxypropyltrimethoxysilane (KBM-5103, produced by Shin-EtsuChemical Co., Ltd.), 123 parts by weight of oxalic acid and 415 parts byweight of ethanol. The mixture was reacted at 70° C. for 4 hours, andthen cooled to room temperature to obtain a transparent silane compoundas a curable composition. The silane compound thus obtained had aweight-average molecular weight of 1,600, and the components having amolecular weight of from 1,000 to 20,000 account for 100% of theoligomerorhigher components. The gas chromatography of the silanecompound showed that 3-acryloxypropyltrimethoxysilane as a startingmaterial had not been left therein.

Preparation of Coating Solution A for Low Refraction Film

The polymer (P-1) according to the present invention was dissolved inmethyl isobutyl ketone in a concentration of 30% by weight. To thesolution was then added a photopolymerization initiator Irgacure 907(trade name) in an amount of 5% by weight based on the solid content toprepare a coating solution A for low refraction layer.

Preparation of Anti-Reflection Film 101

The coating solution for hard coat layer was applied to a triacetylcellulose film having a thickness of 80 μm (TD-80UF, produced by FujiPhoto Film Co., Ltd.) using a gravure coater. The coated material wasdried at 100° C., and then irradiated with ultraviolet ray having anilluminance of 400 mW/cm² from a 160 W/cm air-cooled metal halide lamp(produced by EYGRAPHICS Co., LTD.) at a dose of 300 mJ/cm² while the airin the reaction vessel was being purged with nitrogen to an oxygenconcentration of not greater than 1.0% by volume to cause the coat layerto be cured, thereby forming a hard coat layer having a thickness of 3.5μm.

The coating solution A for middle refraction layer was applied to thehard coat layer using a gravure coater. The coated material was dried at100° C., and then irradiated with ultraviolet ray having an illuminanceof 550 mW/cm² from a 240 W/cm air-cooled metal halide lamp (produced byEYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm² while the air in thereaction vessel was being purged with nitrogen to an oxygenconcentration of not greater than 1.0% by volume to cause the coat layerto be cured, thereby forming a middle refraction layer (refractiveindex: 1.65; thickness: 67 nm).

The coating solution A for high refraction layer was then applied to themiddle refraction layer using a gravure coater. The coated material wasdried at 100° C., and then irradiated with ultraviolet ray having anilluminance of 550 mW/cm² from a 240 W/cm air-cooled metal halide lamp(produced by EYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm² while the airin the reaction vessel was being purged with nitrogen to an oxygenconcentration of not greater than 1.0% by volume to cause the coat layerto be cured, thereby forming a high refraction layer (refractive index:1.93; thickness: 107 nm).

The coating solution A for low refraction layer was then applied to thehigh refraction layer using a gravure coater. The coated material wasdried at 80° C., irradiated with ultraviolet ray having an illuminanceof 550 mW/cm² from a 160 W/cm air-cooled metal halide lamp (produced byEYGRAPHICS CO., LTD.) at a dose of 600 mJ/cm² while the air in thereaction vessel was being purged with nitrogen to an oxygenconcentration of not greater than 1.0% by volume to form a lowrefraction layer (refractive index: 1.43; thickness: 86 nm). Thus, ananti-reflection film 101 was prepared.

Preparation of Anti-Reflection Film Samples 102 to 116

Anti-reflection films 102 to 116 were then prepared in the same manneras in the aforementioned anti-reflection film sample 101 except that (1)the titanium dioxide fine particles to be used in the middle refractionlayer and the high refraction film were changed, (2) the copolymer (P-1)according to the present invention to be used in the low refractionlayer A was changed to P-4, P-5 and P-13, respectively, and (3) thecoating solution A for low refraction layer was replaced by thefollowing coating solution B for low refraction layer as shown in Table6.

Preparation of Titanium Dioxide Fine Particles

A differently surface-treated titanium dioxide fine particles havingother elements incorporated therein was prepared in the same manner asSample 102 except that the preparation of the titanium dioxide fineparticles used and the doping (injection) of cobalt, aluminum orzirconium instead of iron (Fe) and the surface treatment were carriedout according to a known method (JP-A-5-330825). The content of thevarious elements were adjusted such that the ratio of Ti/element (byweight) was 98.5/1.5. The titanium dioxide fine particles thus preparedwas recognized to have a rutile type crystal structure and had anaverage primary particle size of 40 nm, a specific surface area of 38 nmand a specific surface area of. 44 m²/g.

Preparation of Coating Solution B for Low Refractive Index

A heat crosslinkable fluorine-containing polymer having a refractiveindex of 1.42 (Opstar JN7228; solid content concentration: 6% by weight,produced by JSR Corporation) was subjected to solvent substitution toobtain a methyl isobutyl ketone solution of heat crosslinkable fluorinepolymer having a solid content concentration of 10% by weight. To 56.0 gof the aforementioned heat crosslinkable fluorine polymer solution werethen added 8.0 g of a methyl ethyl ketone dispersion of silica fioneparticles (MEK-ST, solid content concentration: 30% by weight, producedby NISSAN CHEMICAL INDUSTRIES, LTD.), 1.75 g of the aforementionedsilane compound, 73.0 g of methyl isobutyl ketone and 33.0 g ofcyclohexanone. The mixture was then stirred. The mixture was thenfiltered through a filter made of polypropylene having a pore diameterof 0.4 μm to prepare a coating solution for low refraction layer.

TABLE 6 Sample No. 101 102 103 104 105 106 107 108 Element in Cobalt ″ ″″ Aluminum Zirconium None Cobalt titanium dioxide Surface Aluminum ″ ″ ″″ ″ ″ None treatment hydroxide and Zirconium hydroxide Low refractionA(P-1) A(P-4) A(P-5) A(P-13) A(P-1) ″ ″ ″ layer Remarks InventionInvention Invention Invention Invention Invention Comparison Invention

TABLE 7 Sample No. 109 110 111 112 113 114 115 116 Element in AluminumZirconium None Cobalt Aluminum Zirconium Cobalt None titanium dioxideSurface None ″ ″ Aluminum ″ ″ None None treatment hydroxide andZirconium hydroxide Low refraction A(P-1) ″ ″ B ″ ″ ″ ″ layer RemarksInvention Invention Comparison Comparison Comparison ComparisonComparison ComparisonEvaluation of Anti-Reflection Film

The various anti-reflection films thus prepared were then evaluated forthe following properties. The results are shown in Table 8.

(1) Evaluation of Haze

The anti-reflection film was evaluated for haze using a haze meter(NHD-1001DP, produced by Nippon Denshoku Industries Co., Ltd.).

(2) Evaluation of Reflectance

The spectral reflectance at an incidence angle of 5° was measured at awavelength of from 380 nm to 780 nm using a spectrophotometer (V-550,ARV-474, produced by JASCO Corporation). The average reflectance at awavelength of from. 450 nm to 650 nm was then determined.

(3) Evaluation of Weathering Resistance

Using a xenon arc lamp type light-resistance testing machine (XF type)which had been conditioned for outdoor average sunshine with aborosilicate glass filer and a quartz filter, a weathering resistancetest was effected at an illuminance of 80 klux on the irradiated surfacein an atmosphere of a black body temperature of 63° C. and a relativehumidity of 50% at an exposure time of 0 hour, 300 hours, 600 hours and900 hours.

The anti-reflection film which had been thus exposed was thenmoisture-conditioned at a temperature of 25° C. and a relative humidityof 60% for 2 hours.

The anti-reflection film was then given a checkerboard cut comprising 11longitudinal lines and 11 crosswise lines, totaling 100 squares, by acutter knife on the surface thereof having a high refraction layer, andthen subjected to adhesion test with a polyester adhesive tape (No. 31B)produced by NIITO DENKO CORPORATION three times on the same site. Theanti-reflection film was then observed for the occurrence of peeling.The results were then evaluated according to the following 4-stepcriterion.

-   -   E: No checkers observed peeled out of 100 checkers    -   G: 2 or less checkers observed peeled out of 100 checkers    -   F: 3 to 10 checkers observed peeled out of 100 checkers    -   P: More than 10 checkers observed peeled out of 100 checkers

TABLE 8 Average reflectance Weathering resistance Sample No. Haze (%)(%) 0 hr 300 hr 600 hr 900 hr 101 0.34 0.34 E E E E 102 0.34 0.35 E F EE 103 0.34 0.35 E E E E 104 0.34 0.34 E E E E 105 0.34 0.35 E E E G 1060.34 0.34 E E E G 107 0.35 0.35 E G P P 108 0.34 0.34 E E E G 109 0.340.34 E E G G 110 0.34 0.34 E E G G 111 0.34 0.34 E F P P 112 0.35 0.34 EG P P 113 0.35 0.34 E F P P 114 0.35 0.34 E F P P 115 0.34 0.34 E F P P116 0.35 0.33 E P P P

It can be seen in Table 7 that an excellent weathering resistance andanti-reflection performance can be realized by the use of ananti-reflection film having a titanium dioxide fine particles accordingto the present invention incorporated in the high refraction layer and afluorine-containing copolymer according to the present inventionincorporated in the low refraction layer. It can be also seen thatcobalt-containing titanium dioxide fine particles which have beensubjected to surface treatment exhibits an excellent weatheringresistance.

In the samples prepared in the same manner as in Samples 101 to 116except that the hard coat layer of Samples 101 to 116 was changed to thehard coat layer used in Examples 6 to 36, the same effect as obtained inSamples 101 to 116 was obtained.

Example 14

Evaluation of Image Display Device

The image display device provided with the anti-reflection film of thepresent invention thus prepared exhibited an excellent anti-reflectionperformance and an extremely excellent visibility.

Example 15

Preparation of Protective Film for Polarizing Plate

A saponifying solution was prepared by keeping a 1.5 N aqueous solutionof sodium hydroxide at 50° C. Further, a 0.01 N aqueous solution ofdiluted sulfuric acid was prepared.

The anti-reflection films prepared in Examples 13 (Sample Nos. 101 to116) were dipped in the above aqueous solution of sodium hydroxide for 2minutes, and then dipped in water so that the aqueous solution of sodiumhydroxide was thoroughly washed away. Subsequently, the anti-reflectionfilms were dipped in the afore-mentioned diluted aqueous solution ofsulfuric acid for 1 minute, dipped in water so that the diluted aqueoussolution of sulfuric acid was thoroughly washed away, and thenthoroughly dried at 100° C.

The anti-reflection films thus saponified were then evaluated forcontact angle with respect to water on the surface of the transparentsupport on the side thereof opposite the side having a high refractionfilm. As a result, the contact angle was not greater than 40 degrees.Thus, a saponified transparent supports were prepared.

Preparation of Polarizing Plate

A polyvinyl alcohol film having a thickness of 75 μm (produced byKURARAY CO., LTD.) was dipped in an aqueous solution comprising 100parts by weight of water, 7 parts by weight of iodine and 105 parts byweight of potassium iodide so that iodine was adsorbed thereto.Subsequently, this film was longitudinally monoaxially stretched by afactor of 4.4 in a 4 wt-% aqueous solution of boric acid, and then driedwhile being tensed to prepare a polarizing plate.

The anti-reflection film (protective film for polarizing plate) of thepresent invention was then adhered to one side of the polarizing platewith a polyvinyl alcohol-based adhesive as an adhesive in such anarrangement that the saponified triacetyl cellulose side thereof wasopposed to the polarizing plate. Further, a triacetyl cellulose filmwhich had been saponified in the same manner as mentioned above wasadhered to the other side of the polarizing plate with the samepolyvinyl alcohol-based adhesive.

Evaluation of Image Display Device

TN, STN, IPS, VA and OCB mode transmission type, reflection type orsemi-transmission type liquid crystal display devices provided with thepolarizing plate of the present invention thus prepared exhibited anexcellent anti-reflection performance and hence an extremely excellentvisibility. These effects were remarkable particularly in VA mode.

Example 16

Preparation of Polarizing Plate

An optically anisotropic optically-compensated film having a disc ofdiscotic structural unit disposed oblique to the surface of thetransparent support which changes in its angle between the disc ofdiscotic structural unit and the surface of the transparent support withthe distance from the transparent support (Wide View Film SA-12B,produced by Fuji Photo Film Co., Ltd.) was subjected to saponificationon the side thereof opposite the side having an optically anisotropiclayer under the same conditions as in Example 15.

The anti-reflection film (protective film for polarizing plate) preparedin Example 15 was then adhered to one side of the polarizing filmprepared in Example 15 with a polyvinyl alcohol-based adhesive as anadhesive in such an arrangement that the saponified triacetyl celluloseside thereof was opposed to the polarizing film. Further, the saponifiedoptically compensated film was adhered to the other side of thepolarizing film with the same polyvinyl alcohol-based adhesive in suchan arrangement that the triacetyl cellulose side thereof was opposed tothe polarizing film.

Evaluation of Image Display Device

TN, STN, IPS, VA and OCB mode transmission type, reflection type orsemi-transmission type liquid crystal display devices provided with thepolarizing plate of the present invention thus prepared exhibited anexcellent contrast, a very wide vertical and horizontal angle of view,an excellent anti-reflection performance and an extremely excellentvisibility and display quality as compared with liquid crystal displaydevices provided with a polarizing plate free of optically compensatedfilm.

These effects were remarkable particularly in VA mode.

ADVANTAGE OF THE PRESENT INVENTION

By preparing a high refraction film containing an inorganic fineparticles comprising as a main component titanium dioxide comprising atleast one element selected from the group consisting of cobalt, aluminumand zirconium, an anti-reflection film excellent in weatheringresistance (particularly light-resistance) can be provided at a lowprice in a large amount.

By preparing a high refraction layer having the constitution of thepresent invention made of a dispersant, a binder and an inorganic fineparticles as described in detail herein by a coating method, ananti-reflection film and a protective film for polarizing plateexcellent in physical strength (scratch resistance, etc.), chemicalresistance and weathering resistance (resistance to moist heat,light-resistance) can be provided at a low price in a large amount.Further, a polarizing plate and an image display device having theaforementioned characteristics can be provided thereby.

1. A high refraction film having a refractive index of from 1.55 to 2.40comprising inorganic fine particles having an average particle diameterof from 1 to 200 nm comprising titanium dioxide as a main component,said titanium dioxide containing cobalt, wherein the film furthercomprises an organic compound binder, and wherein said inorganic fineparticles comprising titanium dioxide containing cobalt are dispersedwith a dispersant.
 2. The high refraction film of claim 1, wherein thecobalt is contained in an amount of from 0.05 to 30% by mass based onthe mass of titanium.
 3. The high refraction film of claim 1, whereinthe cobalt is present in the interior of the inorganic fine particles.4. The high refraction film of claim 1, wherein said inorganic fineparticles have a specific surface area of from 10 to 400 m²/g.
 5. Thehigh refraction film of claim 1, wherein said inorganic fine particlesare coated with at least one compound selected from the group consistingof an inorganic compound, organic metallic compound and organiccompound, which lowers or eliminates photocatalytic activity.
 6. Thehigh refraction film of claim 5, wherein the inorganic compound whichlowers or eliminates photocatalytic activity contains at least oneelement selected from the group consisting of cobalt, aluminum andzirconium.
 7. The high refraction film of claim 5, wherein said at leastone compound which lowers or eliminates photocatalytic activity is anorganic metal compound represented by the following general formula (I)or a derivative thereof:(R¹)_(m)—Si(OR²)_(n)  (I) wherein R¹ represents a substituted orunsubstituted alkyl group or aryl group, R² represents a substituted orunsubstituted alkyl group or acyl group, m represents 0 or an integer offrom 1 to 3 and n represents an integer of from 1 to 4, with the provisothat the sum of m and n is
 4. 8. The high refraction film of claim 1,wherein said dispersant has an anionic group.
 9. The high refractionfilm of claim 1, wherein said dispersant further has a crosslinkable orpolymerizable functional group.
 10. The high refraction film of claim 9,wherein said dispersant has a crosslinkable or polymerizable functionalgroup at the side chain.
 11. The high refraction film of claim 9,wherein said dispersant has a weight-average molecular weight of notlower than 1,000.
 12. A high refraction film having a refractive indexof from 1.55 to 2.40 comprising inorganic fine particles having anaverage particle diameter of from 1 to 200 nm comprising titaniumdioxide as a main component, wherein said titanium dioxide containscobalt, and said titanium dioxide has a rutile crystal structure,wherein the film further comprises an organic compound binder, andwherein said inorganic fine particles comprising titanium dioxidecontaining cobalt are dispersed with a dispersant.
 13. Ananti-reflection film comprising a transparent support and at least oneof a high refraction layer and a low refraction layer formed thereon,wherein said high refraction layer is a layer having a refractive indexof from 1.55 to 2.40 and a thickness in the range of from 30 to 200 nm,wherein the high refraction layer is an optical interference layer, thehigh refraction layer comprising inorganic fine particles having anaverage particle diameter of from 1 to 200 nm comprising titaniumdioxide as a main component, and said titanium dioxide contains cobalt.14. A process for the production of the anti-reflection film of claim13, comprising providing the high refraction film on a transparentsupport.
 15. A protective film for polarizing plate comprising theanti-reflection film of claim 13, wherein the contact angle of thesurface of the transparent support on the side thereof opposite the sidehaving said high refraction film with respect to water is not greaterthan 40 degrees.
 16. A process for the production of the protective filmfor polarizing plate of claim 15, comprising providing the highrefraction film on a transparent support.
 17. A polarizing platecomprising a polarizing film and two protective films having saidpolarizing film interposed therebetween, wherein the anti-reflectionfilm of claim 13 is used as at least one of the two protective films.18. A polarizing plate comprising a polarizing film and two protectivefilms having said polarizing film interposed therebetween, wherein theanti-reflection film of claim 13 is used as one protective film and anoptically compensated film having optical isomerism is used as anotherprotective film.
 19. The polarizing plate of claim 18, wherein saidoptically compensated film has an optically isomeric layer provided onone surface of the transparent support, said optically isomeric layerhas a compound having a discotic structure unit, the surface of a discof said discotic structure unit is oblique to the surface of thetransparent support and the angle between the surface of a disc of saiddiscotic structure unit and the surface of the transparent supportchanges with the distance from the transparent support.
 20. An imagedisplay device having the anti-reflection film of claim 13 disposed onthe image display surface thereof.
 21. An image display device havingthe polarizing plate of claim 17 disposed on the image display surfacethereof.
 22. An image display device having the polarizing plate ofclaim 18 disposed on the image display surface thereof.
 23. Ananti-reflection film comprising a transparent support and at least oneof a high refraction layer and a low refraction layer formed thereon,wherein said high refraction layer is a layer having a refractive indexof from 1.55 to 2.40 comprising inorganic fine particles having anaverage particle diameter of from 1 to 200 nm comprising titaniumdioxide as a main component, wherein said titanium dioxide containscobalt, and said low refraction layer is a layer comprising a cured filmof a copolymer as a main component comprising a repeating unit derivedfrom a fluorine-containing vinyl monomer and a repeating unit having a(meth)acryloyl group in its side chain.
 24. The anti-reflection film ofclaim 23, wherein said copolymer is a copolymer of the following generalformula (III):

wherein L represents a C₁-C₁₀ connecting group, m represents 0 or 1, Xrepresents a hydrogen atom or methyl group, A represents a repeatingunit derived from an arbitrary vinyl monomer and may be constituted of asingle component or a plurality of components, and x, y and z eachrepresent mol % of the respective constituent and represent a valuesatisfying the relationships 30≧x≧60, 5≧y≧70 and 0≧z≧65.
 25. Theanti-reflection film of claim 23, wherein said inorganic fine particlesare coated with at least one compound selected from the group consistingof an inorganic compound, organic metallic compound and organiccompound, which lowers or eliminates photocatalytic activity.
 26. Theanti-reflection film of claim 25, wherein the inorganic compound whichlowers or eliminates photocatalytic activity contains at least oneelement selected from tile group consisting of cobalt, aluminum andzirconium.
 27. The anti-reflection film of claim 25, wherein said atleast one compound which lowers or eliminates photocatalytic activity isan organic metal compound represented by the following general formula(I) or a derivative thereof:(R¹)_(m)—Si(OR²)_(n)  (I) wherein R¹ represents a substituted orunsubstituted alkyl group or aryl group, R² represents a substituted orunsubstituted alkyl group or acyl group, m represents 0 or an integer offrom 1 to 3 and n represents an integer of from 1 to 4, with the provisothat the sum of m and n is
 4. 28. An image display device comprising theanti-reflection film of claim 23 disposed on an image display surfacethereof.
 29. An anti-reflection film comprising a transparent supportand at least one of a high refraction layer and a low refraction layerformed thereon, wherein said high refraction layer is a layer having arefractive index of from 1.55 to 2.40 comprising inorganic fineparticles having an average particle diameter of from 1 to 200 nmcomprising titanium dioxide as a main component, wherein said titaniumdioxide contains cobalt, and said titanium dioxide has a rutile crystalstructure, wherein the film further comprises an organic compoundbinder, and wherein said inorganic fine particles comprising titaniumdioxide containing cobalt are dispersed with a dispersant.
 30. An imagedisplay device comprising the anti-reflection film of claim 29 disposedon an image display surface thereof.